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By R. S. Busk, R. F. Marande

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By R. F. Marande, R. S. Busk

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By Cornelius F. Kelley

SEVENTY-FIVE years ago, in Wilkes-Barre, Pennsylvania, 22 men of vision banded together to initiate this great organization. Ideals and emotions mingled and united in the declaration of a twofold purpose: first, the more economic production of minerals and metals, and second, the promotion of greater safety and welfare for each man so employed-tacit recognition of the inseparability of humanitarian and utilitarian concepts of world progress. The members and honorary members then, as now, were mining engineers and associates from allied walks of life. Under the able guidance of David Thomas, our first president and outstanding ironmaster of the time, there were elected 46 members and associates, and the foundations of the Institute were laid. Conceived in a turbulent postwar era, the problems then faced had some similarity to those we face in this time of war-bashed uncertainty. With a Civil War behind them and once again dedicated to a spirit of national endeavor, they surveyed the landscape, then surged ahead toward a beckoning industrial horizon. That effort has never been relaxed. Poised upon the threshold of a new century, rancher, banker, engineer and businessman paused to contemplate and evaluate his natural endowments. Surrounded by immeasurable God-given wealth, necessity inspired

Jan 1, 1947

By Thomas V. Falkie

These are exciting times for the coal mining community. Although the industry is in the middle of a healthy boom, there are strong forces tending to counteract or at least temper the rate of growth. There are many pushing and pulling factors of interest to mining people, and a few salient ones will be mentioned here. Primarily because of a tremendous demand for energy, a demand that can't be met by other fuels, the coal industry is in boomsville. Another contributing factor to this situation is the increased overseas demand for metallurgical coal. These demands are being counteracted by a lack of people, the lead-time required to develop new capacity and wildcat strikes, among other things.

Jan 1, 1971

WILLIAM YOUNG WESTERVELT, Chairman, Representing A. T. M. E. and M. and M. Soc. of Am. ALFRED G. WHITE, Secretary, Representing U. S. Bureau of Mines. W. 0. HOTCHKISS, Representing Association of American State Geologists. DAVID WHITE, Representing U. S. Geological Survey. The organization and purpose of the War Minerals Committee was explained in a special war notice in the-August Bulletin. The first work of this Committee is to secure and condense information as to the relative importance of different properties from the standpoint of domestic mineral production. When the possibilities of ore deposits are known, involving, in some cases, further examination through the voluntary services of, Engineers and Geologists, then the necessary policy required to stimulate such development can be determined. Proper recommendation has been and will be made to .the various agencies controlling the situation during the war. This will insure a complete presentation of the needs of the situation. Every legitimate effort will be made to stimulate the production of domestic minerals and to put the industries on a permanent basis. The following information forms indicate the type of information required by the Committee. Engineers and Geologists can assist in one of several ways in furnishing information to the War Minerals Committee:

Jan 10, 1917

By Norman Brown, J. V. Rinnovatore

It was found that a shear stress applied during the recovery had no effect on the amount of recovery if the stress was less than the instantaneous yield point irrespective of the direction of the stress. Large ajplied stresses during recovery had a marked effect, which depended on the direction of stressing. Single strain reversals at -72°C not only produced the Bausch-inger effect but also increased the flow stress. The increase inflow stress was attributed to vacancies, which have appreciable mobility at -72 °C. THEORIES I-' of recovery suggest that the internal stress field of the dislocations plays an essential role. Most investigations of recovery use time and temperature as the independent variables; however, here stress has been introduced as a variable in two ways: 1) by varying the internal stress field according to the amount of strain prior to recovery and 2) by applying an external stress during recovery. Tannen- baum and Kauzrnann studied the effect of applying a stress during recovery by measuring the change in creep rate after recovery; they found that stresses as high as 95 pct of the creep stress had no effect on recovery. Earlier, Wood and scrutton6 showed that an applied stress during creep increased the rate of poly-gonization. The experiment by Wood involved poly-crystalline aluminum whereas Tannenbaum and Kauzmann used a single crystal of zinc. In this investigation, zinc single crystals were used and deformed in a manner to prevent polygonization. Thus, the main difference between this investigation and that of Tannenbaum and Kauzmann is the use of the stress-strain curve instead of creep rate as the index of recovery. In addition, the applied stress during recovery varied

Jan 1, 1961

THE committee in charge of arrangements for the meeting of the Institute in September has com-pleted its program. The headquarters of the meeting will be at the Palace Hotel, San Francisco, and the registration committee will be at the hotel all day on Sunday, Sept. 24, and from 8 a.m. until noon on Monday. On Sunday afternoon, automobiles will be available for sightseeing trips around the city. Monday will be devoted to technical sessions. In the morning, there will be sessions on Mining and on Iron and Steel; in the afternoon, sessions on Mining and Milling. At these sessions, in addition to the papers mentioned in the tentative list printed in August, there will be presented three papers on the geology, mining and milling of the Comstock lode; one on the Aztec mine, Baldy, N. M.; one on the Colombian oil fields; and one on charcoal precipitation of cyanide solutions. The luncheon on that day will be Dutch Treat, for men only, at the Engineers Club. On Monday evening, there will be an informal buffet supper at the home of F. W. Bradley. On Tuesday morning, a party of 50 men will leave for Hetch Hetchy. During the four days of the trip, the party will see the Priest tunnel and earth dam under construction by steam-shovel and hydraulic-fill methods, the Big Creek shaft and tunnel, early intake power plant and tunnels and the Hetch Hetchy dam under construction. For those who remain in San Francisco, Tuesday will be "San Francisco Day." There will be motor trips to the Presidio, Cliff House, Golden Gate Park, and other points of interest, and shopping trips to Chinatown. On Wednesday, "University of California Day," the party will be guided through the university by members of the Mining Association, the affiliated stu-dent society, and will see the Greak Theatre and not-able buildings. Thursday will be "Leland Standford, Jr. University Day." Automobiles will leave the Palace Hotel at 10 a.m., and will return from the university at 4.30 p.m. Friday has been reserved for trips to the Selby Smelter, to Mt. Tamalpais, or to other points of interest. Arrangements will be made to visit the mines or gold dredges in California, if members desire to do so, but such trips must of necessity be considered special trips and arrangements will have to be made to suit the convenience of the individual or party. The Golf Committee will make arrangements for those who wish to play golf.

Jan 9, 1922

By W. R. Crane

DRAINAGE in these mines has been discussed in papers, on mining practice,1 but the fact that water, varying from 0.16 to 3.46 and averaging 1.43 times the amount of ore mined, has to be pumped from the mines daily, indicates the importance of the problem and the advisability of making a thorough investigation of the source of mine water, its mode of entry into the mines, its effect upon mining conditions; and consideration of means of improving the conditions. While conditions are not serious, yet there is danger that they may become worse if present mining practice is continued, owing to the presence of formations, known to carry large quantities of water, that overlie the ore bed worked. Much detailed information has been collected regarding: rainfall, and run-off in streams draining the district; the effect of different kinds of formations, porous and non-porous; the inclination of the surface; the condition of the surface above the mines, i. e., whether or not disturbed by ground movement; the occurrence of the ore and character of associated formations, particularly with respect to presence of jointing or slip planes, faults, etc.; failure of top rock in the old stopes; and the conditions under which water effects entrance into the mines, i. e., whether as a natural or forced flow. The study furnished fundamental data on the source of waters now entering the mines and that which may later enter due to collapse of top formations in. abandoned workings. The presence of jointing, or slip planes, has a pronounced influence upon the whole drainage problem. These present lines of least resistance to the water and, by weakening the top formations, cause fracturing of the overlying rock, allowing both surface and deep-seated waters to enter the mines.

Jan 1, 1927

By Arthur Redfield

THE West Indies are the summits of a submerged, mountain chain, the continuation of which must be sought in the mountains of central Honduras. In Haiti, the chain divides, one branch passing through Jamaica and the other through Cuba, the Cayman Islands, and the Misteriosa bank. Suess divides the West Indies into three zones: The first zone is entirely of volcanic origin and includes many recent volcanic cones. It includes the arcùate string of islands, which extends from Saba and St. Kitts to the Grenadines and Grenada. The western half of Guadeloupe belongs to this group. The second zone consists of a geanticline, of which the sedimentary rocks range from the Jurassic to the Quaternary, but consist chiefly of Lower Tertiary sediments. In the west it is broad, including the whole of the Greater Antilles; but in the east it is restricted to a narrow belt, which includes the Virgin Islands (except Anegada), Anguilla, St. Bartholomew, Antigua, the eastern part of Guadeloupe and part of Barbados. The islands that compose the third zone are flat and low. Like the second, this zone is broad in the west and narrow in the east; it includes the Bahamas, Anegada, Sombrero, Barbuda, and part of Barbados. Geologically, Florida and the plain of Yucatan may be regarded as belonging to it. Trinidad and Tobago, though-geographically adjacent to the Lesser Antilles, are geologically a detached part of the South American continent. The crystalline complexes of northern Trinidad and of Barbados are a continuation, en echelon, of the crystalline axis of the promontory of Paria. The folded Cretaceous and Tertiary of the central and southern parts of Trinidad represent a continuation of the folded sediments of the Paria district of Venezuela.

Jan 6, 1922

By E. C. Kersey, R. J. Gennone

MetALLOGRAPHIC investigations of composites of zinc alloys and aluminum have been made to study the effects of various thermal treatments on the zinc-alloy grain size and diffusion of zinc into the core material. The use of various alloys of zinc has necessitated the development of a universal etchant which will allow microscopic examination of the zinc grain size regardless of the composition.

Jan 1, 1960

By R. W. Smith, R. W. M. Lai, J. Leja

J. Leja (Professor, Dept. of Mineral Engineering, U.B.C. Vancouver, Canada) — I would like to offer some comments on the behavior of contact angle with time, treated in this paper. The authors should be congratulated for a clear exposition of these uncommon departures in the correlation between flotation and contact angle, in systems of importance to industrial practice. Some nine years ago Professor J. H. Schulman (presently at Columbia University, New York) and I reported on a similar study conducted at the Ernest Oppenheimer Laboratory, Cambridge, England.' The systems used by us had, how- ever, no direct practical application at that time, as mercury in solutions of xanthates was tested with a variety of alkyl-aryl polyoxyethylene frothers which were then new to flotation practice. Further, the paper dealt with findings contrary to the then widely held belief that the contact angle established in collector-solution is unaffected by the addition of a frother. Correlation with flotation, or lack thereof, was not sought, though we did suggest that in many cases the selectivity of frothers might be influenced by the dynamic contact angles. We also stated (on p. 243,

Jan 1, 1968

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By F. R. Archibald, C. M. Nicholson

The present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay, There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity hut they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the Property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time priding review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3,460,000 The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time Operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1949

By D. F. Coolbaugh

Asia, the largest and most populous continent, has had little political influence on world affairs until very recently. The picture is rapidly changing. Although the cultures of various Asian countries differ widely, today they are united in their desire to industrialize. This desire is the key for expansion of Asian mineral production. The following discussion deals primarily with the situation in the south and southeast Asian countries -India, Pakistan, Burma, Thailand, Cambodia, Laos, South Vietnam, Malaya, and Indonesia.

Jan 10, 1960

By H. Engelmann

THE very extensive development of a brown coal formation, in the region of the Rocky Mountains, is well known to all of you. The existence of these coals was known years ago, but they were of no practical importance until within a few years, when the mineral wealth of that country began to be developed and railroads were built. As their qualities became better known, their adaptability to domestic manufacturing and metallurgical purposes was more appreciated. They are still much undervalued, although they are mined at some points on a very extensive scale. A large portion of this coal formation is of cretaceous age, while it appears to extend into the tertiary epoch; but whatever difference there may be in the ages of these coals of different localities, they all have some common characteristics which distinguish them from our Eastern stone coals of the

Jan 1, 1876

In discussing Mr. Keller's paper, I quoted the results obtained by Mr. Allan Gibb, correctly crediting them to Mr. Gibb, with due reference to the report in which they were published. But in the table immediately following, and in my further remarks, following the table, I find that, by some clerical or other error which I cannot, after the lapse of time, explain, I spoke of Mr. Gibb as Mr. "Dean"—a metallurgist who had written on a related subject, but not on the point I was discussing. In short, my reference throughout was to the work of Mr. Gibb; and by reading a Gibb " for a Dean " in all places on pp. 832 and 835 where the latter name occurs, my remarks will be brought into accordance with my intention, and with the facts.

Jan 1, 1901

By F. Valton

In the number of the Engineering and Mining Journal for April 7th, 1877, Mr. W. P. Ward, of Cartersville, Georgia, explains in a very interesting manner, the results he obtained in the manufacture of ferromanganese in the blast furnace. These results may be summed up as follows : Production in the blast furnace of an alloy containing 67.2 per cent. manganese and 3 per cent. of carbon at most, with a utilization of the manganese amounting to 58 per cent. With the exception of the indicated proportion of' carbon, which should be almost doubled to express the true state of facts, we would have had no observations to make on Mr. Ward's paper had he taken into account the results obtained in the same line in other centres of production. Before 1870, spiegel with 8 or 10 per cent. manganese only was known among blast-furnace products. In a journey to Sweden, in 1871,I ascertained that the Schysshyttan works manufactured regolarly a spiegel with 18 per cent. manganese. Later, at the Vienna Exhibition, in 1873, the Sava and Jauerburg works, in Carniola, presented to the jury a ferromanganese, obtained in the blast fur-

Jan 1, 1879

By P. Pietrokowsky

RECENTLY a comprehensive investigation of the various sigma binary alloys was published by Duwez and Baen.1 It was shown that the following conditions are necessary for the formation of the sigma phase: (1) the difference in atomic diameters of the two alloying metals must not be more than about 8 pct; (2) of the two elements which form sigma, one must exhibit a body-centered cubic structure while the second metal must be face-centered cubic, at least in one of its allotropic forms. In addition, a tetragonal unit cell was proposed and powder patterns of six sigma phases were indexed for d spacings greater than 1.640 kx. Since the indexing, based on tetragonal symmetry, led to only fair agreement, the possibility of sigma being orthorhombic was investigated. Various methods for indexing orthorhombic powder patterns are de- scribed in the literature.' The method used in this investigation was a graphical examination of the differences in values of sin' 9 for the adjacent lines of the powder diffraction pattern. This method led to a complete indexing of the Cr-Co (60-40) pattern. Because of the strong similarity between the various sigma alloys, it was then possible to assign indexes to the patterns of Fe-Cr (50-50), Fe-Cr-Mo (30-30-40), Fe-V (50-50), Co-V (50-50), and Ni-V (50-50). The values of sin' 9 and indexes of the six sigma alloys, together with visually estimated intensities, are presented in table 1. In general, the similitude between the six patterns is quite good. For spacings greater than 1.75 kx a few differences are noticeable. In the Ni-V pattern, no (320) exists and the two strong lines (030) and (031) are separated by only two lines of lower intensity, unlike any of the other sigma patterns. However, very little is known about the Ni-V phase diagram and it is possible that the equal atomic percentage composition in this system lies in a two-phase region. At lower spacings there is a close analogy between the patterns. The planes

Jan 1, 1951

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By Heribert Wiedemeier, Ali Khan

The tetnperature-conposition phase diagram of the syste,n MnS-CdS has been investigated over a range fro)n 600° to 1000° C. The small degree of solid solution on the MnS rich slde cornpared to the large CdS rich single-plzase region could be esplained by the difference in strzrctures of the cotnponents and the relative sizes of the metal ions. The change in lattice parameter as a function of cot)zposition is linear atzd jollous Vegavd's rule within experittzental limits of error. Mns and CdS have gained considerable attention in recent years because of their interesting solid state properties. In order to investigate such properties and thermodynamic quantities of mixed compositions of transition metal chalcogenides, it is necessary to establish their phase diagrams. Two earlier publications are concerned with the MnS-CdS system. Schnaase' found complete miscibility when MnS and CdS were co-precipitated in aqueous solutions at room temperature. However, there is evidence that the mixed crystals were not stable over the entire range of composition. roger's' investigation of the ternary system ZnS-CdS-MnS at 900" C indicates a solution of 48 mole pct MnS in CdS. During the course of this work which covers a temperature range from 600" to 100O° C, emphasis has been placed on the use of high-purity materials and well-defined modifications of starting products. EXPERIMENTAL Starting Materials. The stable green modification of MnS with NaCl structure was prepared by direct fusion of the elements and by chemical transport reaction. Stoichiometric amounts of manganese of 99.99+ pct purity and of sulfur of 99.999 pct purity from Gallard-Schlesinger Corp. were sealed in an evacuated quartz tube at a pressure of 10"5 mm Hg and annealed for 48 to 60 hr at 800°C. The quartz tubes used throughout this work were outgassed under high vacuum at a temperature of 90OU to 1000° C for 12 to 18 hr. For the synthesis of MnS by chemical transport3 stoichiometric ratios of elemental manganese and sulfur and small amounts of iodine were sealed under vacuum in a quartz tube, which was placed in the temperature gradient, 900/800-C, of a two zone furnace. Single crystals of MnS in form of platelets and octahedra were deposited at the cooler end of the tube. The manganese content was determined by EDTA titratin. A typical result of several analyses was 63.05 pct Mn which agreed well with the computed value, 63.14 pct. Commercially available CdS of 99.9+ pct purity, a mixture of the cubic and hexagonal forms, was converted into the hexagonal high-temperature modification by annealing CdS under vacuum in quartz tubes at 700° C for about 36 hr. As a second method, cadmium sulfide was transported in a temperature gradient, 70O° /650" C, with in vacuo sublimed iodine from the hot to the cooler zone of the tube. Large sized crystals in form of hexagonal columns and some platelets were obtained. An average result of the cadmium analysis by EDTA titration4 was 77.93 pct in good agreement with the computed value, 77.81 pct. Only the NaCl modification of MnS and the wurtzite modification of CdS were used for the solid solutions. Preparation of Solid Solutions. Finely powdered MnS and CdS samples were thoroughly mixed in molar ratios and compressed into pellets of about 6 mm diam and 2 mm in height at a pressure of approximately 13,500 atm.

Jan 1, 1969