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By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By M. K. Geer, H. F. Yancey

Investigations of the fundamental factors involved in the performance of various coal-cleaning processes have constituted a substantial portion of the research 011 coal cleaning conducted by the Bureau of Mines. These detailed studies of the mechanism of separating coal from impurity in various cleaning devices were undertaken to provide the coal industry with information that is helpful in selecting the type of cleaner most suitable for treating a particular coal. Previous reports describing these investigations have dealt with the wet table,1 the pneumatic table,' and the plunger,3 pulsator.4 and Baum types5 of jigs. The present report compares the performance of three commonly used units treating the same coal—a pneumatic jig, also known as the air-flow. cleaner, a pneumatic table, and a Baum-type jig. Object and Plan The fact that pneumatic coal-cleaning processes are less efficient than wet-washing methods because they are unable to make as sharp a separation between coal and impurity is well recogilized. The literature, however, contains little quantitative in- formation on the relative performances of the two types of cleaners. The object of the present report is to present a detailed comparison of the performances of two pneumatic units and one wet-washing process treating coal from the same bed. Although the information in this report demonstrates that the performance of the pneumatic cleaners is not as good as that of those employing water, it must not be construed as reflecting on the usefullless of such equipment. Performance is often secondary to other factors in the selection of coal-cleaning equipment, and the advantages inherent in pneumatic processes frequently outweigh the limitations imposed by their performance. Specific gravity and particle size are the principal factors that influence the separation of coal from impurity in either pneumatic or wet processes; consequently, the tools available for this investigation were the float-and-sink bath and the screen. Accordingly, the raw coal, clean coal, and refuse samples representing the operation of each type of cleaning unit were first separated into a series of density fractions by means of the float-and-sink bath, and then each density fraction was screened into a series of size fractions. By this procedure the raw coal, clean coal, and refuse were subdivided into components of restricted ranges in density and size. From these data it was possible to determine how the cleaning unit disposed of each component of the raw coal; that is. what proportion of each component is sent to clean coal or rejected as refuse.

Jan 1, 1947

By H. F. Yancey, M. K. Geer

Investigations of the fundamental factors involved in the performance of various coal-cleaning processes have constituted a substantial portion of the research 011 coal cleaning conducted by the Bureau of Mines. These detailed studies of the mechanism of separating coal from impurity in various cleaning devices were undertaken to provide the coal industry with information that is helpful in selecting the type of cleaner most suitable for treating a particular coal. Previous reports describing these investigations have dealt with the wet table,1 the pneumatic table,' and the plunger,3 pulsator.4 and Baum types5 of jigs. The present report compares the performance of three commonly used units treating the same coal—a pneumatic jig, also known as the air-flow. cleaner, a pneumatic table, and a Baum-type jig. Object and Plan The fact that pneumatic coal-cleaning processes are less efficient than wet-washing methods because they are unable to make as sharp a separation between coal and impurity is well recogilized. The literature, however, contains little quantitative in- formation on the relative performances of the two types of cleaners. The object of the present report is to present a detailed comparison of the performances of two pneumatic units and one wet-washing process treating coal from the same bed. Although the information in this report demonstrates that the performance of the pneumatic cleaners is not as good as that of those employing water, it must not be construed as reflecting on the usefullless of such equipment. Performance is often secondary to other factors in the selection of coal-cleaning equipment, and the advantages inherent in pneumatic processes frequently outweigh the limitations imposed by their performance. Specific gravity and particle size are the principal factors that influence the separation of coal from impurity in either pneumatic or wet processes; consequently, the tools available for this investigation were the float-and-sink bath and the screen. Accordingly, the raw coal, clean coal, and refuse samples representing the operation of each type of cleaning unit were first separated into a series of density fractions by means of the float-and-sink bath, and then each density fraction was screened into a series of size fractions. By this procedure the raw coal, clean coal, and refuse were subdivided into components of restricted ranges in density and size. From these data it was possible to determine how the cleaning unit disposed of each component of the raw coal; that is. what proportion of each component is sent to clean coal or rejected as refuse.

Jan 1, 1947

By A. Cochardt, D. H. Feisel

HE success of the sintered aluminum powder material (SAP)' in raising the maximum useful temperature of aluminum alloys has stimulated effort in investigating similar systems in which the metallic matrixes have higher melting points. Examples of such systems which have been studied are nickel-alumina,2, 3copper-silica,4 copper-alumina,4 titanium-cerium oxide,5 and 80/20 nickel-chromium,8 cobalt,= and molybdenum7 matrixes with various hardeners. Conventional precipitation-hardened high-temperature alloys are often thermally unstable in service. The original fine particles that are responsible for good strength properties grow in size at elevated operating temperatures, a process termed "over-aging." This growth of precipitated particles causes a gradual loss in strength properties. A previous paperb describes the factors that govern the process of overaging, and estimates the time required for overaging of a nickel-alloy matrix dispersion-hardened by various precipitates such as are found in current high-temperature alloys, and by alumina. These calculations indicate that nickel-base alloys hardened with Ni3Al, Tic, or TiN are quite unstable at 1340" F (727°F). Such alloys should overage within a few hours at that temperature. A nickel-base alloy hardened with alumina, on the other hand, should behave differently. It should not overage appreciably within a thousand years. It was further shown8 that the thermal stability of the oxide-hardened alloy is mainly due to the low solubility of oxygen in equilibrium with alumina in the nickel-base matrix. Since the oxygen solubility is small, little oxygen can diffuse, and structural changes require very long times. This paper illustrates the effects of time and temperature on the structural stability of nickel alloy matrixes hardened by dispersions of Ni3A1, Ni3Ti, Tic, and alumina, and of nickel-chromium matrixes hardened by alumina. Hardness measurements and metallography have been used as a measure of structural stability. EXPERIMENTAL PROCEDURE Using the best information from published phase diagrams,'-l4 compositions of the Ni-Al, Ni-Ti, and Ni-Ti-C alloys were determined so as to have 5 vol pct of precipitate at 1350° F(732°C), the temperature selected to illustrate the effect of time on structural stability. Table I lists the chemical compositions of these alloys. Standard laboratory melting and alloying techniques were used in preparing ingots of the F-Series of alloys. The cast ingots, 1 3/4 in. in diam, were forged to 3/8-in. diam rods.

Jan 1, 1960

By F. L. Ruhlman, Max C. Eastman

The termination of the recent war marked a major changc in the oil-field operations at. Elk Hills. Production was greatly curtailed, various experimental production projects were started, and a long-range exploratory program was inaugurated. Production was reduced from the wartime peak of 65,000 bbl per day to the current rate of about 8ooo bbl per day in order to maintain an available source of crude that can be drawn upon during a national emergency. The existing production rate is deemed essential to carry on the experimental production projects. These projects are being conducted to determine the best methods and means of maintaining the Reserve, shut in, but in a state of readiness to produce the maximum quantity of oil in the most expeditious manner. Projects now being investigated include: (I) protection of surface equipmerit; (2) repair of wells that might damage the reservoir; (3) gas injection; (4) water eneroachment, (5) gravity drainage. An exploratory program is being carried on to determine the amount of recoverable oil in the unexplored portions of the Reserve. The Shallow-zone exploration is practically completed, but owing to the complexity of the Stevens structure and the magnitude of the oil discoveries in the Stevens, exploration will probably continue in that zone for another two years. Introduction Summary of Development History of Elk Hills Although a detailed history of Elk Hills oil field is presented in various publications,1,2 a summary of its unusual development and production history will be given in order that the present problems may be more readily understood. The first development that resulted in commercial production was in the central part of the Reserve. The first well, Hay No. I, in sec 36-R,* was completed in January I9I9, and was soon followed by 37 Others in the same general area. It is commonly referred to as the Hay-Carman area and was shut in in stages from 1925 to 1934 as a result of litigation regarding the title to the land. Not being highly producti,, only about 6½ million barrels of oil with a large volume of gas was produced from the area prior to the shutdown. Shortly after the start of the development of the Hay-Carman area, drilling was started 6 miles east in sec 36-S' Tupman NO. I came in for 5000 bbl per day early in I92o, It was followed by more than 200 others in the next few years, and the field became one of major importance. Produc-

Jan 1, 1949

By H. R. Deeth, C. J. Koenig

About ten years ago nepheline syenite was introduced to the ceramic industry and the material has now found application in the various branches of the industry, namely, as a vitrifying agent in white-wares and as a source of alumina and alkalies in glasses, glazes, and porcelain enamels. Spencel described the early mining and processing developments regarding this material. Since the time of his article many research papers have appeared relating to the usage of nepheline syenite but little has been published relative to subsequent mining and processing methods. A complete indexed review of the literature was issued recently by Ohio State University.2 Since "Lakefield" nepheline syenite from Blue Mountain, Ontario (Fig I); is the only commercial ceramic-grade nepheline syenite now being marketed on this continent, discussion is limited to this operation carried on by American Nepheline Limited, Lakefield, Ont., and its subsidiary in the United States, American Nepheline Cory. at Rochester, N. Y. The Deposit Blue Mountain is a long ridge rising to an elevation of about 350 ft at its highest point above the surrounding country and extending for about six miles in a northeasterly direction across Methuen township, Peterborough County. The rock of the Blue Mountain central alkaline intrusive is fine grained, light colored and of even granitic texture. The solidified mass consists predominately of the minerals albite, nepheline and microcline in order of abundance. The average mineralogical composition for the deposit obtained by a study of 112 samples taken regularly over the whole formation is as follows:3 Volumetric Mineral Per Cent Albite.................... 54 Microcline................ 20 Nepheline................ 22 Muscovite................ 2 Mafics.................... 2 (Biotite, hastingsite, magnetite) Total................... loo The mineral nepheline (or nephelite) belongs to the feldspathoid group but is lower in silica content than are the feldspars. It is a silicate of soda, potash, and alumina (NaKAl2O32SiO2). Its presence with albite (Na2oA12O3 6SiO2) and microcline (K2O A12O3 6SiO2) gives the Blue Mountain deposit an alkali content of 15 pct and an alumina content of approximately 24 pct. While this huge alkaline mass is somewhat variable mineralogically, it has a uniform chemical composition. When the iron, mostly in the form of magnetite, is removed during processing, a remarkably uniform finished product is obtained. Geological surveying has disclosed many million tons of nepheline syenite in the Blue Mountain deposit. Diamond drilling in the area where mining is now being carried out indicates a block of about one million tons.

Jan 1, 1949

By A. F. Brock

The cut-and-fill mining methods in use in the mines of The International Nickel Company of Canada Limited, at Falconbridge Nickel Mines Limited, in the Sudbury District, and at McIntyre Porcupine Mines Limited in the Porcupine District, are typical of the general cut-and-fill practice in both the base-metal mines and the gold mines in the Province of Ontario. The following pages describe the methods in use. HORIZONTAL CUT-AND-FILL STOPING Horizontal cut-and-fill stoping, as practiced in the mines of The International Nickel Company of Canada Limited, falls into two main classifications: (I) transverse cut-and-fill stoping, where ground conditions or wide ore bodies make it necessary to establish narrow stopes and pillars across the width of the ore body; (2) longitudinal cut-and-fill stoping where ore body widths and ground conditions allow safe mining of the full width of the ore body. Transverse Cut-and-fill StopiNg General Stoping Layouts Stope and Pillar Widths.—For transverse stoping, experience has indicated that narrow stopes and pillars, 27 ft. 6 in and 22 ft., respectively, are most satisfactory. These width are multiples of 5 ft. 6 in., which is the center to center dimension of a standard square set. Thus any stope, or block of stopes, can be readily converted from cut-and-fill to square set-and-fill if ground conditions should warrant such a change. Formerly, pillars were established 16 ft. 6 in. wide, the equivalent of the width of three square sets, with the intention of extracting the pillars by mining an overhand slice one set wide and an underhand slice two sets wide. However, subsequent experience proved that a two-set overhand slice is so much more efficiently mined than a one-set slice, and 22-ft. pillars have been made standard. Chutes.—The stope chutes are established on the longitudinal center line of the stopes and are spaced at 22-ft. centers from footwall to hanging wall. The footwall chute is usually from 5 to 10 it. from the footwall of the stope. It is offset where necessary at an angle of 52° and vertical chutes are carried from the offset at 22-ft. centers. In sections of the ore body where a flat hanging wall would cut off hanging-wall chutes within a few cuts of the sill, it has proved to be more economical to use temporary chutes or slushers, or both, for these first few cuts, rather than to el permanent chutes at the hanging wall.

Jan 1, 1946

By T. E. Leontis, R. S. Busk

WORK was initiated several years ago at The Dow Chemical Company to determine the applicability of powder metallurgy processes to magnesium and its alloys. Although it was found possible to apply the normal techniques of compacting and sintering, it was discovered early that the technique of extrusion offered special promise. This technique and the alloys produced were therefore studied extensively, and the present paper is a partial report of those studies. It is expected that a second paper will discuss more extensively some of the alloy systems simply mentioned here. Although the literature on powder metallurgy is very extensive, there are only two articles dealing with magnesium13,14 and there is no reference to the direct extrusion of the powder of any metal without the preliminary step of compacting. Furthermore, no mention has been made of the possibility of designing alloys by the technique of powder extrusion, particularly alloys that cannot be made in any other way. Sauerwaldl3 discusses the extrusion of magnesium and aluminum powder to produce alloys containing nonequilibrium phases, but again he emphasizes the importance of pre-compacting before extrusion. There seems to be general agreement that some form of hot-pressing is essential to obtain in a compact the full theoretical density of the metal used.'-" The nearest approach to the technique of direct powder extrusion is that of extrusion of pre-sintered compacts,'-" for which the best review through 1944 is that by Kieffer and Hotop.11 Ensign* discussed a specialized technique of "extruding" already compacted and sintered gears for the purpose of sizing. Sauerwa1d13 discussed the compacting and extrusion of magnesium and magnesium-aluminum alloy band-saw chips. The properties of the extruded compacts were found to be comparable with those of extrusions prepared from solid billets. He also extruded a compacted mixture of magnesium and aluminum powder and found the properties to be somewhat different from those obtained on an extrusion made from a cast billet of the same composition. The second reference dealing specifically with the powder metallurgy of magnesium is Stern's patent," in which is described the extrusion of scrap chips and turnings following a hot-pressing and sintering step. Considerable emphasis in most of these articles is placed on the necessity of atmospheric protection to minimize the danger of oxidation. Experimental Procedure The first experiments were made with the small extrusion press shown in fig. 1. With this press, billets of about 1/2 in. diam are used to produce wire

Jan 1, 1951

By H. R. Deeth, C. J. Koenig

ABOUT ten years ago nepheline syenite was introduced to the ceramic industry and the material has now found application in the various branches of the industry, namely, as a vitrifying agent in white-wares and as a source of alumina and alkalies in glasses, glazes, and porcelain enamels. Spence1 described the early mining and processing developments regarding this material. Since the time of his article many research papers have appeared relating to the usage of nepheline syenite but little has been published relative to subsequent mining and processing methods. A complete indexed review of the literature was issued recently by Ohio State University.2 Since "Lakefield" nepheline syenite from Blue Mountain, Ontario (Fig I); is the only commercial ceramic-grade nepheline syenite now being marketed on this continent, discussion is limited to this operation carried on by American Nepheline Limited, Lakefield, Ont., and its subsidiary in the United States, American Nepheline Corp. at Rochester, N. Y. THE DEPOSIT Blue Mountain is a long ridge rising to an elevation of about 350 ft at its highest point above the surrounding country and extending for about six miles in a northeasterly direction across Methuen township, Peterborough County. The rock of the Blue Mountain central alkaline intrusive is fine grained, light colored and of even granitic texture. The solidified mass consists predominately of the minerals albite, nepheline and microcline in order of abundance. The average mineralogical composition for the deposit obtained by a study of 112 samples taken regularly over the whole formation is as follows:3 [VOLUMETRIC MINERAL PER CENT Albite54 Microcline20 Nepheline22 Muscovite2 Mafics2 (Biotite, hastingsite, magnetite) Total100] The mineral nepheline (or nephelite) belongs to the feldspathoid group but is lower in silica content than are the feldspars. It is a silicate of soda, potash, and alumina (NaKAl2O32SiO2). Its presence with albite (Na2O A1203 6SiO2) and microcline (K20 A12O3 6SiO2) gives the Blue Mountain deposit an alkali content of 15 pct and an alumina content of approximately 24 pct. While this huge alkaline mass is somewhat variable mineralogically, it has a uniform chemical composition. When the iron, mostly in the form of magnetite, is removed during processing, a remarkably uniform finished product is obtained. Geological surveying has disclosed many million tons of nepheline syenite in the Blue Mountain deposit. Diamond drilling in the area where mining is now being carried out indicates a block of about one million tons.

Jan 1, 1947

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By G. M. Schwartz, J. N. Gundersen

Utilization of magnetite-bearing taconite from the great Mesabi range of Minnesota is fast becoming a major industry in the state. The planning and early development stages of taconite processing projects have been de-scribed1-3 and an excellent discussion has appeared recently4 concerning the current mining, crushing, concentrating, and pelletizing techniques of the Reserve Mining Co., whose operations lie entirely within the Eastern Mesabi district. The present paper will deal only with some of the geological aspects of taconite utilization in the district, with emphasis placed upon some of the common mineralogical and textural features of the tacon-ites currently being mined or stripped and how these factors generally affect the potential recovery of the iron from the metamorphosed Biwabik iron-formation. The generalized geologic setting of the Eastern Mesabi district is presented in Fig. 1. The small circles on the geologic map, adapted from Grout and Broderick,3 mark the location of drill holes that were available for inspection during this study through the courtesy of Reserve Mining and Erie Mining Cos. The cores from these holes were divided into stratigraphic units and examined for their mineral content. Typical mineral associations and grain fabrics were also determined from hundreds of thin and polished sections. Available metallurgical tests made it possible to determine the probable response of a given variety of taconite to magnetic concentration. The longitudinal section of Fig. 1, projected along the strike of the iron formation, presents the simple stratigraphy of the area. It also shows the uniformly thick nature of the iron formation members in the district as well as a somewhat abrupt thickening of the formation to the west of the probable fault. The stratigraphy of these precambrian rocks has been described5-' elsewhere and need only be briefly reviewed. Historically, the oldest rocks unit, the Giants Range granite (Algoman) was covered by the Animikie group of sediments (Middle Huronian?), consisting of the Pokegama, Biwabik, and Virginia formations. Outcrops of the Pokegama quartzite are locally distributed along the northern limit of the Biwabik iron formation, but they are too limited to depict on the geologic map of Fig. 1. The effects of the intrusion of several small diabase sills within the Virginia and Biwabik formations are obscure because all of these rocks have been subsequently highly metamorphosed, mainly by the Duluth gabbro. The emplacement of the transgressing Duluth gabbro (Middle Keweenawan) and that of numerous peg-matitic veins in the iron formation8 has resulted in extensive contact and metasomatic metamorphism which has locally reconstituted the previously existing minerals of the Biwabik formation, in large part quartz and magnetite, into a wide variety of silicate mineral assemblages9 that have a profound effect upon the re coverability of the remaining magnetite. The entire region has subsequently been eroded and largely buried beneath Pleistocene glacial deposits. Structurally, the strike of the gently dipping Animikie group generally parallels the elongate outcrop pattern of the Biwabik iron formation on the map of Fig. 1. The Animikie group most commonly dips from 5" to 15" to the south-southeast. In this area, the Duluth gabbro pluton is somewhat sill-like, dipping about 30" to the southeast. Projecting these present structures upward, it seems probable that the gabbro once extended over the underlying Animikie group in the Eastern Mesabi district. SELECTION AND PRESENTATION OF DATA Because of the locally intense metamorphic activity in the district, mineralogical variations within the magnetite-bearing taconites are commonly abrupt, both vertically and laterally. Consequently it is difficult to select a single hole or small group of holes whose cores will be entirely representative of all of the district. Two holes have been selected, however, that in a general way represent mineralogical and textural variations that are likely to be encountered in both the eastern and western parts of the district. These recently drilled holes were chosen for discussion because it was possible to log the core and then to place the sample intervals at stratigraphic boundaries prior to preparation of the core for magnetic tube tests.

Jan 1, 1961

By Steve H. Carpenter, Henry E. Otto

The explosive welding of metals is dependent upon the production of a jetting action caused by the collapsing of one metal plate against another. Successful welds are generally accomplished if the yield strength of the metals is in the range of 10,000 to 90,000 psi and the sonic velocity of the metal is greater than the detonation velocity of the explosive if direct contact explosive is being used.' Should the detonation velocity exceed the velocity of sound in the metal it may still be possible to obtain the jetting action and a good weld. However, in most cases where a high detonation velocity is used complications arise because of reflected shock waves which tear the bond apart as fast as it is put together.' Explosive welding of lead presents several problems since its yield strength and sound velocity are very low. Various values have been published3-5 for the velocity of sound in lead ranging from 2000~ to 23004 m per sec. Most of the high-order explosives have detonation velocities on the order of 6000 to 8000 m per sec, which precludes their use. The dynamites have a lower detonation velocity of around 2800 m per sec which is still somewhat too high. Lower-order explosives such as ammonium nitrate (1070 m per sec) must be used to weld lead in the as-received condition if the explosives are used in direct contact. Rather than use low-order explo'sives it was decided to alter the sonic velocity of the lead. The sonic velocity is directly related to the modulus of the material according to the following expression: Fig 1—Interface of explosive weld of lead to steel. Lead is on top As-polished Magnification 75 times as well as the yield strength. Bolling et al. 6 show that the shear modulus of lead single crystals increases from about 0.72 X1011 dynes per sq cm at 300°K to about 0.98 X1011 dynes per sq cm at 0°K, an increase of approximately 3 5 pct. This gives an increase in the sonic velocity of around 700 m per sec. Hence, the sonic velocity of lead at cryogenic temperatures is approximately equivalent to the detonation velocity of the low-order dynamites. We have obtained high-quality lead to steel explosive welds using a 40 pct dynamite in direct contact with the lead. Prior to detonation the lead was chilled with liquid nitrogen (78°K) to increase the strength and sonic velocity. Welds were made while the lead was cold. Specimen sizes were 3 by 6 in. A preset angle of 5 deg with a 0.10-in. standoff at the base was the geometrical setup used. The amount of explosive used for optimum welding of an 1/8 -in. -thick lead sheet to a steel plate was found to be 7 g per sq in. A PETN sheet explosive line wave generator was used to insure a linear detonation front through the dynamite. A photomicrograph of a lead-steel weld is shown in Fig. 1. The typical wave effect that constitutes a good explosive weld is present. When tested in shear, the weld failed in the lead, indicating that the bond is stronger than the lead base metal. Higher-order explosives were also tried without success. We believe this indicates the importance of matching the detonation velocity and the sonic velocity for successful explosive welding. Note Added in Proof. High quality explosive welds of lead to steel have recently been obtained at ambient temperature using a low velocity (1000 M per sec) free running dynamite. The weld interface obtained is comparable to Fig. 1. 'S. H. Carpenter, R. H. Wittman, and R. J. Carlson: Proceedings of the First International Conference of the Center for High Energy Forming, Syracuse University Press, syracu.se, N. Y., in press. 'A. HI Holtzman and G. R. Cowan: Welding Risearch. Council Bull., No. 104, April, 1965. 'Metals Handbook, 8 ed., p. 1062, Metals Park, Ohlo. 'J. M. Walsh, M. H. Rice, R. G. McQueen, and F. L. Yarger: Phys. Rev., 1957, vol. 108, pp. 196-216; 'L. V. Al'tshuler, K. K. Krupnikov, B. N. Ledener, V. I. Zuchikhin,

Jan 1, 1968

By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953

By Leon T. Eleiel

Ten years ago a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the application of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these isolated bits of information can be ascertained, the message begins to take meaning. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his interpretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty—the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1937

By Leon Eliel

TEN years ago .a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these. isolated bits of infor-mation can be ascertained, the message begins to take meaning.. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

By Leon Eliel

TEN years ago a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these isolated bits of infor-mation can be ascertained, the message begins to take meaning. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of, a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern .he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

By N. S. Stoloff, R. G. Davies

A study has been made of the efject oj different dislocation-precipitate interactions upon the temperature dependence of the flow stress of aged Ni-14 at. pct A1 alloy. It is observed that when the dislocations bow between widely spaced (-20004 coherent Ni3Al particles the flow stress decreases with increasing temperature in the normal way. However, when the dislocations cut closely spaced (-5004 particles the flow stress is independent of temperature from -100 to 600°C, due to a balance between softening of the matrix and an increase in strength of the particles with increasing temperature. The retention of strength at high tempera-tures of commercial nickel-base alloys, which are strengthened by the precipitation of a phase based upon Ni3Al, is thought to be due to the unusual strength properties of Ni3Al. The flow stress of Ni3Al increases continuous1y from -196"C to a maximum at -600"C. It is concluded from a series of thermal-mechanical tests that the sevenfold increase in flow stress over this temperature interval is due to a lattice effect and is not diffusion-controlled. The flow stress of precipitation- or dispersion-hardened materials depends on the resistance to dislocation motion within the matrix and the extra energy required for dislocations to bow between or to cut particles. If the dislocations bow between the particles or if the strength of the cut particles is constant with temperature, then the flow stress of the precipitation-hardened alloy must decrease with increasing temperature due at least to the decrease in elastic modulus of the material. There will be softening also from thermally activated cross-slip or climb, offering an additional degree of freedom for dislocations to avoid particles. For example, in the case of nickel containing a dispersion of thoria,' which most probably deforms by dislocations bowing between particles, the flow stress decreases by about 50 pct between 25" and 650°C. In A1-Cu alloys2 aged to produce the 8" precipitate, dislocations cut the particles, and the flow stress decreases by about 20 pct between -269" and 25°C. However, many commercial high-temperature nickel-base alloys, for example Inconel-X and Udimet-700, exhibit little or no decrease in flow stress with increasing temperature up to about 700°C. A characteristic feature of these alloys is that they are strengthened by the precipitation of a phase based upon Ni3A1. Guard and westbrook4 and flinn' have shown that Ni3Al (and alloys in which a third element such as molybdenum or iron is substituted for part of the aluminum) is unusual in that the hardness and flow stress increase with temperature to a maximum at about 600°C. For the flow stress of a precipitation-hardened alloy to be independent of temperature we propose that the particles must be cut by dislocations moving through the matrix and that the strength of the particle must increase with increasing temperature. Theories of precipitation hardening do not take into account the flow stress of the dispersed particles that are cut during deformation; the only dissipative process usually considered7 is the creation of interface within the particle and between the precipitate and matrix. The purpose of the present investigation has been to study in detail the temperature dependence of the flow stress of a nickel-base alloy strengthened by the precipitation of Ni3Al in two structural conditions such that when deformation occurs it does so by dislocations a) bowing between the particles and b) cutting the particles, respectively. A simple binary Ni-14 at. pct A1 alloy was chosen because considerable information is already available for this system concerning phase equilibria and precipitation reactions and rates.' Dislocation-precipitate interactions in the binary alloy should be similar to those in the more complex commercial alloys. In addition, the mechanical and physical properties of NisAl were studied in detail in the hope of elucidating the mechanism by which the strength increases with increasing temperature up to 600°C. EXPERIMENTAL PROCEDURE For the study of the effect of precipitation of Ni3A1 upon the temperature dependence of the flow stress, an alloy containing 14 at. pct A1 was utilized; a Ni-8 at. pct A1 solid-solution alloy was employed as a comparison material. Vacuum-cast ingots were hot-rolled at 1000°C and cylindrical compression samples, 0.20 in. diam by 0.40 in. high, were prepared from the 1/4-in.-diam rod. Specimens were recrystallized and solution-treated at 1000°C for 1/2 hr and then water-quenched. A preliminary study revealed that, when the Ni-14 at. pct A1 alloy was aged for 1 hr at 700°C, significant precipitation hardening was obtained, and that the structure was free from grain boundary discontinuous precipitation; an overaged condition was produced by annealing the aged specimens at 850°C for 1 hr. To circumvent the difficulties involved in the hot rolling and swaging of Ni3A1, compression samples,

Jan 1, 1965

By A. J. Heckler, J. A. Peterson

A capsule technique was successfully employed to investigate the effect of nickel on the activity of nitrogen in Fe-Ni-N austenite in the temperature range 600" to 1200°C. This technique consisted of equilibrating nitrogen among various Fe-Ni alloys within a sealed silica capsule. Nitrogen transfer among the specimens occurred by N, gas at 900°, lOOO? and 1200?C. Nitrogen gas pressures within the capsules were estimated to be as high as 22 atm. The activity coefficient of nitrogen, fN , in Fe-Ni-N austenite is adequately described by the linear interaction equation: log . wt pct Ni where the standard state is chosen such that fN = I as wt pct Napproaches zero in binary Fe-N. This relationship was determined over the temperature range 873" to 1473°K and for nickel contents of 0 to 35 wt pct. ALTHOUGH chemical thermodynamics of liquid iron alloys have been extensively studied, experimental data for the solid state are needed. These thermody-namic data will provide a basis for understanding phase transformations, precipitation reactions, metal-gas equilibria, and so forth. The interaction of sub-stitutional alloying elements with the interstitial elements is of particular interest. In this investigation the thermodynamic behavior of Fe-Ni-N austenite has been studied. The solubility of nitrogen gas in iron austenite is known to obey Sieverts&apos; law up to about 65 atm.1-6 In addition, the solubility of nitrogen in Fe-Ni austenite has been investigated5"8 using the classical method of equilibrating Fe-Ni alloys with nitrogen gas at 1 atm. A capsule technique similar to that used to study the activity of carbon in alloyed austeniteg&apos;&apos;&apos; was employed in the present work to determine the effect of nickel on the activity of nitrogen in Fe-Ni austenite over the temperature range 600" to 1200°C. EXPERIMENTAL PROCEDURE A series of Fe-Ni alloys up to 35 wt pct Ni was vacuum melted and cast into 1 by 3 by 6 in. ingots. Chemical analyses at the top and bottom of each ingot demonstrated that the ingots were homogeneous with respect to nickel content. The nickel contents are given in Table I. Additional chemical analyses showed that wt pct Si < 0.05, s < 0.01, C < 0.01, Al < 0.006, 0 < 0.004, Mn < 0.002, and P < 0.002. A 2 in. section of each ingot was cold rolled to 0.015 in. The material was then decarburized to a carbon content of less than 0.004 wt pct. A portion of the material of each nickel content was nitrided to various levels in a H2-NH3 gas atmosphere to provide a source of nitrogen during subsequent equilibration. The experimental technique consisted of equilibrating the series of Fe-Ni-N alloys in a partially evacuated sealed silica capsule at the temperature of interest. Both Vycor and quartz capsules were used. In general, the final equilibrium nitrogen content for each Fe-Ni alloy was approached from both higher and lower nitrogen levels. The criterion for establishing that equilibrium was attained was that the final nitrogen content for each Fe-Ni alloy was the same irrespective of the initial level. A schematic drawing of the sample configuration in a capsule is shown in Fig. 1. The samples were arranged so that there was a minimum of physical contact. The samples were also dusted with a fine, high purity alumina powder to help prevent sticking. Several different types of furnaces were used in this study. In each case, a thermocouple was placed immediately adjacent to the capsule during equilibration and the temperature was controlled to within *4?C of that reported. At each equilibration temperature, the following times were found to be more than sufficient to attain equilibrium: 600°C-250 hr, 900°C-150 hr, 1000°C-150 hr, and 1200°C-50 hr. After equilibration the capsules were quenched in water and the nitrogen contents of the specimens determined by a Strohlein analyzer. Analyses of samples after equilibration at 1000" and 1200°C showed no silicon pickup from the silica capsules. RESULTS AND DISCUSSION Transfer Mechanism. The mechanism by which nitrogen was transferred among specimens in an initially hydrogen flushed and partially evacuated capsule equilibrated at 1000°C was investigated. After equilibration the gas in the capsule was collected over water and an estimate of the pressure at temperature

Jan 1, 1970

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,&apos; only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,&apos; and that the solid solution is quite limited in the MnO-MnS system.&apos; The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1&apos; and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969