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By J. Waldman, M. B. Bever, A. K. Jena

The heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of one solid solution have been measured by tin solution calorimetry. The heats of formation are analyzed in terms of the quasichemical theory. If the enthalpy diffel-ence between a hypothetical fcc form and the hcp form of cadmium is taken into account, this analysis does not lead to the conclusion put forth in the literature that electronic effects make significant contributions to the heats of formation of silver-rich Ag-Cd solid solutions. The temperature dependence of the heats of formation is appreciable and negative near 78ºK, but decreases gradually to nearly zero abore 400°K. The relative partial enthalpies per grarn -atom of silver at 541°K and cadmium at 532" and 541°K in tin have also been determined. THE composition range of the silver-rich Ag-Cd solid solutions stable at room temperature extends to about 40 at. pct Cd. Heats of formation of these solid solutions at 308" and 723°K have been measured by solution calorimetry.1,2 Heats of formation for an average temperature of 800°K have also been calculated from vapor pressures.2,3 The heats of formation deviate from the values predicted by the quasichemical theory above about 30 at. pct Cd. This deviation has been attributed to electronic effects at the Brillouin zone boundaries.2 The heats of formation of Ag-Cd alloys are essentially the same at 308", 723", and 800°K; consequently the temperature dependence of the heat of formation d?H/dT = ?Cp is vanishingly small, although from the exothermic heats of formation a negative value would have been expected. In the investigation reported here the heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of 1 solid solution have been measured by tin solution calorimetry. The results are analyzed in terms of the quasichemical theory and the dependence of the heats of formation on temperature is discussed. The relative partial enthalpies per gram-atom of silver in tin at 541" and cadmium in tin at 532" and 541°K were obtained in the course of this investigation. The values of the temperature dependence of the relative partial enthalpies per gram-atom of silver in tin derived from the data reported by various investigators2,4-9 are contradictory. The literature contains only a value for 517°K of the relative partial enthalpy per gram-atom of solid cadmium in tin.2 EXPERIMENTAL PROCEDURES Samples of Ag-Cd solid solutions were prepared by melting weighed amounts of silver (99.99 pct pure) and cadmium (99.95 pct pure) in graphite crucibles under a flux of molten potassium chloride.10 The solidified ingots were sealed in evacuated Vycor tubes and annealed at 775°K for 10 days. The ingots were swaged and drawn into wires. The wires, sealed in evacuated Pyrex tubes, were held at 725°K for 5 hr and cooled to 365°K at an average rate of 2.5ºK per hr, followed by furnace cooling to room temperature. Chemical analysis of samples taken from different parts of each ingot gave no indication of segregation. Metallographic examination showed the samples to be homogeneous. Samples of the solid solutions or of the component elements were added to tin-rich baths in a calorimeter." At the start of a run the bath consisted of pure tin. Silver was used in the form of wire of 0.01-in. diam as supplied and cadmium in the form of lumps. Gold (99.999 pct pure) was added with the samples in order to reduce the endothermic heat effect of additions of Ag-Cd solid solutions. Samples of only one composition were added in a run and the ratio of the weight of alloy to that of gold was the same in all additions of a given run. In each run several calibrating additions of tin were made from 273°K. The heat contents of tin were calculated from the following equation, which is based on published data:12 (HTºK- H279º) = 6.70 T - 72,300/T + 20 cal/gram-atom; 505°K < T < 650°K The heat effect of each addition was plotted against the average of the sum of the atom fractions of solutes in the solution before and after that addition. The total concentration of solutes at the end of a run was less than 2 at. pct. In this range the heat effect was a linear function of the atom fraction of the solutes. The heat effect at infinite dilution and the composition dependence of the heat effect were obtained from the plots. RESULTS AND DISCUSSION Evaluation of Data. The linear dependence on composition of the heat effects of additions suggests that in the dilute range the enthalpy interaction coefficients other than the first-order coefficients of silver, cadmium, and gold are negligible, as shown in a concurrent publication.13 The heat effects at infinite dilution and the values of the composition dependence of the heat effects are listed in Table I.

Jan 1, 1970

By C. A. Stickels, C. M. Yen

Secondary recrystallization was investigated in vacuum-melted electrolytic iron to which 70 pm N was vacuum-meltedadded. The secondary texture is "near {554}<225>" for material cold-rolled 75 to 90 pct, the sharpness of the texture increasing with increased rolling reduction and with decreased annealing temperature. At reductions of 95 and 97.5 pct the secondary texture is &apos;"near {322)(296)". Both secondary orientations also exist as major components of the primary re-crystallization texture. Development of a strong "near {554) (225)" secondary texture appears to depend on the evolution of the Primary texture to a transition texture depleted in orientations near the secondary orientation before the onset of secondary growth. A variety of qualitative experinzents have been used to show that nitrogen is important in limiling primary grain growth. The presence of nitrogen does not seem essential for the establishment of a transition texture, but a loss of nitrogen during annealing may facilitate growth of grains in the secondary orientation. Secondary grains we shown to form initially at the specimen surface. This is not thought to indicate that surface energies are important in the growth process. It is proposed that the quasi-two-dimensional character of surface grains permits discontinuous growth parallel to the surface before secondary growth of interior grains is possible. An earlier study of recrystallization textures in 90 pct cold-rolled electrolytic iron showed that secondary recrystallization occurred after annealing for several days at 700C1 This type of secondary recrystallization, which had not been reported previously, results in the formation of a strong texture, best described by the indices "near {554}(225)". The purpose of the present work was to investigate the effect of various processing variables on secondary recrystallization in this material and determine the mechanism of secondary grain growth. LITERATURE REVIEW An understanding of the mechanism of a secondary recrystallization process depends on knowing: 1) how grains in the secondary orientation come to be in the primary recrystallization texture; 2) why normal grain growth does not occur; and 3) what factors determine the strength of the secondary texture. For secondary growth of grains of a particular orientation, a certain minimum fraction of the grains must be in that orientation after primary recrystallization. This requirement is apparently satisfied "naturally" in certain systems, i.e., when the primary texture obtained by rolling and recrystallizing material initially randomly oriented contains a sufficient fraction of primaries in the secondary orientation. However, in other cases, e.g., {110}<001> and {100}<001> secondary growth in silicon iron,2 it is necessary to enhance the fraction of primary grains in the secondary orientation by rolling and recrystallizing textured material. In the present case, the "near {554}<225>" orientation is contained within the spread of orientations found in the primary recrystallization texture of iron or bbc iron-base alloys. In systems where the main driving force for secondary growth is the reduction in total grain boundary energy, secondary growth is observed only when normal grain growth is minimized. Four ways in which normal grain growth can be limited are: 1) Limitation by a strong primary texture. When a very strong primary texture consisting of a single component or twin-related components develop, most primary grains are separated from one another by relatively immobile small-angle grain boundaries. The classic instance of this is secondary growth into the primary cube texture in some fcc metals. 2) Limitation by precipitates. Precipitates present in the proper volume fraction with a suitable dispersion will limit primary grain growth. The role of MnS inclusions in impeding normal grain growth in Si-Fe is well-documented.5 3) Limitation by sheet thickness. Normal grain growth slows drastically when the mean grain diameter is of the same order as the sheet thickness. This effect has been used to obtain secondary recrystallization in thin sheets of high-purity silicon iron.&apos; 4) Limitation by solute impurities. It is well-established that certain impurity elements in solution can have a large effect on grain boundary mobility.&apos; However, there does not seem to be any secondary recrystallization process in which primary grain size stabilization has been shown to be due to the drag exerted on grain boundaries by dissolved impurities. In certain systems, e.g., secondary recrystallization in silver,&apos; the means by which normal grain growth is limited has not been identified, and solute-impurity limitation might be suspected. In order to understand the factors which determine secondary texture strength in three-dimensional growth, it is necessary to examine in more detail the current picture of general secondary recrystallization processes. Following Cahn,9 it is assumed that the primary grains have a range of sizes and that secondary growth of one of the large grains in this distribution is possible when it exceeds a critical size with respect to its neighboring grains. The critical size depends on the ratio ?S/?p, where ?s is some sort of average grain boundary energy between the potential secondary and the primary grains and ?p is some sort of average grain boundary energy between primary grains. For a constant primary grain size, the critical size for secondary growth increases as ?$/?p increases. May and Turnbull5 have incorporated the

Jan 1, 1969

By Robert W. Elayer

In August 1973, Fluor Utah, Inc. was awarded a contract by the Office of Coal Research (now part of the Energy Research and Development Administration), Department of the Interior, for the examination of the unique problems of large-scale surface coal mining to supply coal conversion complexes. The project consists of two phases: (I) data base development and organization and the formulation of a mathematical computer modeling system for surface mining; and (II) computer manipulation of the data base in accordance with the model to formulate several typical preliminary mine and preparation plant designs. Phase I is scheduled for completion by the end of July 1975 and Phase II is scheduled to be complete by the end of January 1977. This paper briefly discusses the effort for only one aspect of this project-the foundation for geologic modeling developed in Phase I. The Phase I task of geologic modeling can be broken down into two subtasks: (1) identify areas containing sufficient resources of surface-minable coal to support at least one large-scale mining complex, and (2) characterize the coal deposits in these areas for computer storage and retrieval. Identification of Resource Regions The basic production design criteria for large-scale surface mining, as stated in the contract, is the production of 75,000 tpd, or more, of bituminous coal. Based on a constant total Btu delivered to the preparation plant, daily production requirements for the different coals are as follows: Bituminous Coal 75,000 tons Subbituminous Coal 99,500 tons Lignite 143,500 tons Although surface mining on this scale is presently non-existent, it is deemed that future operations, in order to meet the increased energy demands, will have to look forward to much larger scale mining complexes. These tonnage requirements are meant to be used only for the delineation of general areas suitable for large-scale surface mining, termed "Strippable Coal Resource Regions." They were determined largely from the latest complete detailed coal resource estimates of the U.S. Bureau of Mines. Nine strippable coal resource regions, containing over 100 billion tons of strippable coal resources, were identified [(see Fig. 1)]. The delineation of these regions was based entirely upon estimates of surface-minable coal resources and the production design criteria for large-scale surface mining. If surface-mined coal was combined with underground production, or if smaller production rates were specified, then other areas which were omitted here would be included in the regions. Changing the outline of the regions, however, would not add any new mining situations to be studied in Phase II. Characterization of Coal Deposits The second subtask involved the general characterization of the coal deposits contained in the strippable coal resource regions. The geological information gathered

Jan 1, 1976

I do not think too much emphasis can be placed upon creation of favorable climate for development of foreign mineral resources to feed the hungry maw of our industrialized nation. We have become dependent, not only upon the ten raw products indicated in Mr. Bancroft&apos;s article, but upon 71 mineral substances listed by DMPA as in short supply. Forty-four of these are metals, 9 are chemical minerals and 18 are nonmetallic minerals. Of this list only 8 are produced in any large quantity in the United States, and all are vital in peace-time industry. Even more, they are absolutely essential for defense. This represents our present needs. But if our consumption and requirements are projected over the next 25 years as is done by the President&apos;s Materials Policy Commission-The Paley Report-our future outlook becomes appalling. The divergence of consumption over production, even allowing for substitution and conservation, will widen in the future. This means our dependence upon foreign raw materials, mainly minerals, will grow. What are the chief foreign sources of minerals for our future needs? They are chiefly Latin America and the dominions and colonies of the Western European nations. The British Commonwealth countries contain in abundance those minerals which the U. S. lacks. Of 32 of the most critical minerals the Commonwealth is deficient in 7 and lacks only 1; whereas the U. S. is deficient in 18. Strikingly, our deficient minerals are abundant in the Commonwealth and several of their deficiencies are in excess in the U. S. Resources of the two nations complement each other. If Europe should be overrun by an unfriendly power that could control the destinies and resources of the European dominions and colonies, our industrial life would be placed in severe jeopardy. Therefore, I heartily endorse Mr. Bancroft&apos;s statements regarding the Point IV program, provided the program is wisely administered and implemented. It is from the underdeveloped countries, as pointed out by Mr. Bancroft, that most of our future mineral supplies will have to come. Many of the underdeveloped source countries are African colonies and dominions of Western European nations. Our present aid to Europe, therefore, is not, as many infer, a purely one-sided affair; it safeguards our future industrial development and security. Development aid directly to the underdeveloped countries through a well administered Point IV program, can do much, I believe, to safeguard our prosperity. I regard it as a wise investment for future U. S. mineral needs. Dr. Alan M. Bateman Department of Geological Sciences Yale University Mr. Howland Bancroft&apos;s article, The Broadening Road to Foreign Investment, appeared on page 666 of the July MINING ENGINEERING.

Jan 1, 1952

By H. E. Stauss

THE time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at 1100°C. better than did 10 per cent iridium- platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at 1100°C. Platinum alloys in their service at high temperatures encounter conditions some- what similar to those that exist in the usual form of the time-to-fracture "l test with steel. This paper is intended primarily to present results obtained by a "time-to- fracture" test under conditions approximating actual service for platinum (at the temperature 1100°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with lo per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., 1000°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,4 using as heating unit a small, horizontal, platinum- wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life-that is, the time-to-fracture-was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fracture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking stresses drop very rapidly to a small frac-

Jan 1, 1943

By F. W. Newhall, L. N. Plein

During the latter part of the year 1931, the Republic mine of the Republic Steel Corporation, at Republic, about 4 miles south of Brownsville, Pa., was mining coal along four rib or fracture lines. One of these lines, the west butt rib line, was retreating towards a concrete-lined air shaft, 320 ft. deep, which had been sunk in 1911 for ventilation purposes. With the normal rate of mining at that time, it was expected that this rib line would pass the shaft in three or four months and the shaft would then be abandoned and allowed to cave. Realizing the opportunity presented for the study of an unusual case of ground movement, the question of conducting the study was presented by the junior author to thechairman of the Institute&apos;s committee on Ground Movement and Subsidence, Mr. George S. Rice, who presented the matter to Mr. G. H. Morse, General Manager of the Northern Mines, Republic Steel Corporation, and he agreed to cooperate with the Bureau of Mines in making the study, the results of which arc presented in this paper. Acknowledgments are due to Mr. Morse for his full cooperation in this work and to Mr. G. S. Rice and Mr. J. W. Paul, both of the U. S. Bureau of Mines, for their advice and guidance during the course of the work. The authors are indebted to Mr. B. F. Herbert, mining engineer, Northern Coal Mines, Republic Steel Corporation, who assisted in all the surveys, and Mr. W. H. Smith, draftsman, U. S. Bureau of Mines, who prepared all illustrations for publication. Geologic Conditions The shaft is at Merrittstown, which is about one mile northwest of Republic. The topography in the immediate vicinity of Merrittstown consists of rolling country dissected by the meanders of Dunlap Creek and its tributaries. The surface slopes of the hills are gentle and their average gradient is less than 6º. The area at the point where the study was made lies on a hillside sloping towards the southwest, the gradient, varying from 1º to 14º. Fig. 1 shows contour lines at 5-ft. intervals on

Jan 1, 1936

By L. N. Plein, F. W. Newhall

During the latter part of the year 1931, the Republic mine of the Republic Steel Corporation, at Republic, about 4 miles south of Brownsville, Pa., was mining coal along four rib or fracture lines. One of these lines, the west butt rib line, was retreating towards a concrete-lined air shaft, 320 ft. deep, which had been sunk in 1911 for ventilation purposes. With the normal rate of mining at that time, it was expected that this rib line would pass the shaft in three or four months and the shaft would then be abandoned and allowed to cave. Realizing the opportunity presented for the study of an unusual case of ground movement, the question of conducting the study was presented by the junior author to thechairman of the Institute&apos;s committee on Ground Movement and Subsidence, Mr. George S. Rice, who presented the matter to Mr. G. H. Morse, General Manager of the Northern Mines, Republic Steel Corporation, and he agreed to cooperate with the Bureau of Mines in making the study, the results of which arc presented in this paper. Acknowledgments are due to Mr. Morse for his full cooperation in this work and to Mr. G. S. Rice and Mr. J. W. Paul, both of the U. S. Bureau of Mines, for their advice and guidance during the course of the work. The authors are indebted to Mr. B. F. Herbert, mining engineer, Northern Coal Mines, Republic Steel Corporation, who assisted in all the surveys, and Mr. W. H. Smith, draftsman, U. S. Bureau of Mines, who prepared all illustrations for publication. Geologic Conditions The shaft is at Merrittstown, which is about one mile northwest of Republic. The topography in the immediate vicinity of Merrittstown consists of rolling country dissected by the meanders of Dunlap Creek and its tributaries. The surface slopes of the hills are gentle and their average gradient is less than 6º. The area at the point where the study was made lies on a hillside sloping towards the southwest, the gradient, varying from 1º to 14º. Fig. 1 shows contour lines at 5-ft. intervals on

Jan 1, 1936

By G. Ansel, J. P. Doan

THE important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holub1-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength, and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British. Patent 5111376 relates to the parent discoveries of Sauerwald, Eisen¬reich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature" has been found to the particular characteristics of wrought Mg-Zn-Zr alloys, with which the present paper is concerned. - The work to be discussed represents essentially an extrusion study of the Mg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metal¬lography, and toughness of these alloys. Compositional variations are limited to the ranges o to 7 per cent Zn and o to I per cent Zr. EXPERIMENTAL PROCEDURE Alloying and Casting Alloying ingredients were cell mag¬nesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl2 and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manu¬facturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zir¬conium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux¬inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1946

By Fred P. Dewey

IN preparing material for the exhibit of the National Museum at the New Orleans Exposition in 1881, it was decided to attempt to photograph the interior of a coal-mine, in order to get a strictly truthful representation of a thick coal-seam, and to show incidentally the methods of mining. While we have many drawings, both mechanical and artistic, illustrating the subject, they are not satisfactory for these purposes, simply because they are drawings. Aside from this, much interest attaches to pictures of inaccessible places, and the enlarged copies (30 inches by 40 inches) of the photographs we succeeded in obtaining, have attracted a large amount of attention from the visitors to the Museum. The Kohinoor colliery, Shenandoah City, Pa., was selected as most suitable for the attempt, principally on account of the fine exposure of the Mammoth bed, and the comparatively level character of the workings, in that colliery. This is one of the many anthracite-mines of the Philadelphia and Reading Coal and Iron Company. A detailed section of the fiftyfoot or Mammoth bed in this colliery is as follows: Feet. Inches. 1 0 Clod. 1 7 0 Coal. 1 0 Slate. Top Split. 8 0 Coal. 1 6 Slate divider.* 6 0 Coal. 1 0 6 Slate. 2 6 Coal. 0 5 Slate. 1 8 Coal. 1 2 Charcoal. 5 0 coal. 1 0 Bone and Coal. „ „ Coal. [ Bottom Split. 0 6 Bone and Slate. 3 0 Coal. 0 10 Bone and coal. 1 2 Coal. 0 2 Bone. 4 4 Coal. 0 1 Bone. 0 8 Coal.

Jan 1, 1888

By A Andersen

DURING an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investiga-tion was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this sys-tem as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa&apos;s6 and M. Okamoto&apos;s7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. S. Smith&apos;s latest work on the copper-silicon system8 was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter&apos;s diagram and ours checked in all essen-tial features, except the temperature of the peritectic line above 830° C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centered cubic with a lattice constant of 2.848 A.. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexag-onal phase, and to avoid confusion this designation will be adhered to in the present paper.

Jan 1, 1939

By J. W. Freeman, R. F. Decker

A microstructural investigation was pursued to establish the mechanism of the pronounced benefits of traces of boron and zirconium on creep properties of a 55 Ni-20 Cr-15 (20-4 MO-3 Ti-3 A1 alloy at 1600°F. The mechanism of improvement of creep properties was found to be a pronounced stabilizing effect of traces of boron and zirconium on the grain boundaries of the alloy. The alloy with low boron and zirconium was subject to rapzd agglomeration of M23 C6 and in the grain boundaries, followed by depletion of y &apos; and intergranular microcracking at the grain boundaries transverse to applied stress. Brittle fracture then occurred by linking of microcracks. However, additions of zirconium, boron, and boron plus zirconium decreased this tendency in that order, allowing longer creep exposure and higher creep defor.mations before fracture occurred. VERY little information has been published describing the mechanism by which trace amounts of boron or zirconium improve the creep properties of complex nickel-base heat-resistant alloys, although the effect is now well recognized.1-4 Because the phenomenon is so important to properties and the effects are so striking, a study was made of the mechanism in a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 A1 alloy. It was believed that such a mechanistic approach would increase knowledge in theory of alloying and give a more basic understanding of alloy design to resist creep. The basic premise of the study was that boron or zirconium would alter the microstructural characteristics controlling creep and fracture to the extent that the effects could be identified by light and electron microscopy and by electron diffraction techniques. Characteristic of the microstructure of the Ti + Al-bearing nickel-base alloys is the dispersed precipitation of the intermetallic compound Ni,(Al, Ti), the ? &apos; phase, which is generally con- sidered to be the major source of high creep resistance.5-7 In addition, carbide phases have been identified8-10 and these can alter creep properties markedly.11 Since both the ?&apos; and carbide transformations have been found to control properties, careful attention was paid to the effect of boron and zirconium on these transformations.

Jan 1, 1961

By Thomas L. Kesler

Present Raw Materials The lithium industry has had exceptional growth since publication of the last edition of this volume, and the present scale of mining and consumption of raw materials is a great many times that of 1949. The materials of present economic importance consist of four pegmatite minerals and lithium-bearing brine. Spodumene, a lithium pyroxene, occurs in greatest abundance, and is the chief source. It has the formula LiAlSi2O6 and theoretically may contain 8.03 pct Li2O, but in the more important deposits the content is 6.5 to 7.5 pct. The hardness is 6.5, the specific gravity 3.1 to 3.2, and the color mostly pale green to white although deep green, lilac, and yellow varieties exist. The crystals are prisms with strongly developed longitudinal cleavages, and crushing characteristically produces lath-shaped particles. Giant crystals up to 47 ft long are known, but in most occurrences the predominant size range is 0.5 to 12 in. long and 0.1 to 2 in. wide. Hypogene* alteration has formed lithia-bearing sericite and coarser muscovite and rarely eucryptite, while supergene* alteration yields kaolinite and hydrous mica. Lepidolite, of second importance, is a mica of varying composition approximating K2Li3-A14Si7O21(OH,F)3. It has lamellate cleavage, book structure, and a specific gravity of 2.8 to 3. The books range in size from microscopic to a diameter of several inches. The color is mostly violet, but other colors include pink, gray, yellow, and white. Most commercial lepidolite contains 3 to 4 pct Li20 and chemically is in the higher grade range of a series of lithium micas that includes polylithionite, zinnwaldite, and protolithionite. In this series, the content of Li2O is exceptionally as high as 7 pct. Petalite and amblygonite are also of economic importance, but are used in smaller amounts. Petalite has the formula LiA1Si4O10 and is white, gray, or pink. The hardness is 6, the specific gravity 2.4, the cleavage in two planes 114° apart, and the Li2O content commonly 3 to 4.7 pct with a maximum of 4.88. Amblygonite has the formula LiA1FPO4 in which OH may substitute for F to form montebrasite. It is white and has polysynthetic twinning in two directions at 90°. Amblygonite superficially resembles potash feldspar, but has a bluish or grayish tint unlike the cream or salmon tint of the feldspar.[t] The hardness is 6 and the specific gravity 3 to 3.1, and the content of Li2O is the highest among lithium minerals that occur in significant quantity, ranging mostly from 7.5 to 9 pct with a maximum of 10.2. The brine of Searles Lake in California30 has been a commercial source of lithium since 1938. See Chap. 7, p. 108. The "lake" is a saline evaporite deposit, and the exposed part has an area of 12 sq mi. To an average depth of 71 ft, this part of the deposit consists of crystalline salts with 50 pct interstitial voids. The voids are filled with brine that contains mainly sodium and potassium compounds, but the brine also contains 0.015 pct Li2O, which is recovered as dilithium sodium phosphate containing 21 pct Li20. This deposit overlies a

Jan 1, 1960

By N. H. Harrison, J. K. Rodgers, S. Regier

This paper presents comparisons of data obtained from a laboratory reservoir study and from a calculated behavior prediction with the actual production history of a condensate reservoir. A small non-commercial discovery was depleted under closely controlled conditions and the well fluids were sampled at frequent intervals. Data on the reservoir and production variables were accumulated on a fixed schedule. A laboratory reservoir study war made using the initial well fluid samples as charging stock. The production procedures and operating conditions were held constant throughout the study wherever possible and in general paralleled the field work. The well fluid compositions and the cumulative recoveries ar a function of the reservoir pressure were also calculated using conventional flash vaporization procedures and equilibrium constants. Comparisons based on the composition of the well fluid show good agreement, the laboratory study agreeing within experimental accuracy with the field work and the calculated data comparing equally well. The gas-oil ratios are also in good agreement, but with somewhat greater deviations at the higher pressures. In the overall picture, it is believed that a model st,~tiy can predict within experimental accuracy the production history of a condensate reservoir. Better equilibrium constants for the heavier hydrocarbons are needed in order to attain improved composition accuracy by calculation. INTRODUCTION In Aug., 1955, a gas condensate well was completed in San Juan County, Utah, that was initially thought capable of good commercial production. These conclusions were derived principally from core data and electric logs, which indicated good permeability, porosity and gas content. However, after the usual series of potential tests it was found that the reservoir pressure had declined some 22 per cent, and it was obvious that the zone tapped was but a small pocket or trap. It became apparent that, with a controlled depletion of a small reservoir, a unique opportunity was available to compare laboratory and calculated studies with an actual field depletion and to further the present knowledge of condensate reservoirs. FIELD WORK The Coalbed Canyon Well No. 1 was conventionally completed in the Paradox limestone formation to a total depth of 5,912 ft. The producing zone from 5,762 to 5,806 ft was perforated with four jet shots per ft. The wellhead and field equipment were also conventional, the major items consisting of a two-pass indirect fired line heater, a high- and a low-pressure separator with the necessary controls and accessories, gas meters, back-pressure regulators, flare stacks and condensate stock tanks. The initial testing of this well con-sisted of a series of flow potential and pressure build-up tests during which some 30 MMcf of gas was produced. The reservoir pressure declined from an estimated 2,300 to 1,782 psig during this period, from which it was concluded that the reservoir was very small. In order to approach steady-state conditions in the reservoir and so provide optimum conditions for making comparisons, the field depletion was programmed to approach, if possible, constant production conditions. Bi-hourly readings were taken of the tubing pressure, the pressure and temperature of the separators, oil and gas rates, and other pertinent operating data. The gas rate, as indicated by the orifice meter, was held constant by the adjustment of the choke in the line heater. The temperature of the first stage separator was held constant by adjustment of the line heater jacket temperature. Practical considerations of production made the maintenance oi a constant gas rate impossible. The test started with a gas rate of 4 MMcf/D and a separator pressure of 250 psig. This rate was maintained until the choke was fully opened. The gas rate then declined with the falling tubing pressure and production was continued until the rate was about 2

By T. E. Scott, R. P. Zerwekh

The charactevistics of the deformatiotz of fcc thorium were examined between 78 and 473 K. Activation energy, actiuation volume, and the temperature dependence of the flow stress were determined and conlpared uith several theories for the rate-controlling mechnnistn of the tempemture-dependent component of the flou~ stress. It was established that the Cottrell-Stokes law does not hold, even approximately, for thorium. Through consideration of the above factors and other parameters, it was concluded that the vandom solute barrier theory proposed by Friedel demonstrates the best agreement with experimental observations of the deformation of thorium below ambient temperature. THORIUM, the first metal in the actinide series of rare-earth elements, is interesting and important from two points of view. In the more practical vein, it is a potential reactor fuel. As such, it is important to know its properties. Of specific interest here are the mechanical properties of thorium. Second, no detailed information concerning the deformation characteristics of the actinide elements has been gathered to date. In view of the interesting physical and chemical properties of these metals, their mechanical behavior might reveal characteristics which could improve our understanding of the mechanisms controlling deformation of the more common metals. For example, it has been shown1 that thorium exhibits a yield point which is greatly enhanced by interstitial solute elements such as carbon. This is not a normal occurrence in fcc metals. The goal of this investigation, therefore, was to characterize the deformation of polycrystalline thorium. MATERIAL AND PROCEDURES Thorium, made by the magnesium intermediate alloy process described by Peterson et al.,2 was rolled and swaged to 0.065-in.-diam wire. The metal analysis is given in Table I. After preparation, the oxygen and nitrogen contents had risen to 308 and 60 ppm, respectively. The 0.065-in.-diam wires were cut into 2-in. lengths and annealed in a vacuum of lo-&apos; Torr at 750°C for 1 hr, producing a grain size of 2735 grains per sq mm. The ends of the 2-in. sections were masked off so that a 1-in. gage length could be electropolished. Specimens were polished at 35 v in a solution of 6 pct perchloric acid in methanol which was maintained at 0°C . The gage diameters after polishing were about 0.0625 in. The tests were run on a screw-driven tensile machine at a constant crosshead speed corresponding to a strain rate of 0.005 min-&apos;. The strain rate was changed rapidly after each 0.01-in. extension between 0.005 min-&apos; and one of three higher strain rates which were selected in order to achieve strain-rate ratios of 5, 10, and 20. Tests were run at several temperatures from 78" to 473°K; most were tested at 423", 300°, 215", and 78°K. EXPERIMENTAL RESULTS Flow Stress vs Strain and Temperature. Typical true stress-true strain curves for thorium are shown in Fig. 1 for several temperatures over the range 473" to 78°K. The curves for 78", 215", 300") and 423°K were obtained from strain-rate change tests using the lower (0.005 min-&apos;) or base strain-rate values of stress. Additional tests, using the same base strain rate at different strain-rate ratios, gave curves which virtually superposed on those shown, indicating that strain-rate changes did not materially influence the work-hardening characteristics at the base strain rate. The curves for 273") 373") and 473°K were standard tensile tests at 0.005 min-&apos;. The behavior of the flow stress with temperature is

Jan 1, 1968

By Franklyn W. Oatman

In order that the conditions which obtain in an oil well may be readily understood, a brief description of a typical California well and a number of the phenomena accompanying same will be given. That the necessity for the exclusion of water be realized, the effects of water intrusion, a description of methods of prevention, .and a discussion of causes of failure will be presented, followed by a summary and recommendations. Fig. 1 shows a section of a typical well which illustrates the relation of oil sands to overlying strata. It indicates a deep water sand separated from the oil sand by shale, and the proper place for the final shutting off of water. In this well a comparatively thick stratum of compact shale protected the oil from overlying water so that the operation of landing the water string was a simple matter. In some wells the protecting stratum may be only from 3 to 5 ft. thick and very careful operation is necessary in order to land the water string of casing properly and not puncture through to the oil sand. The cases just cited are common, but occasionally, after excluding overlying water, productive oil sands are drilled through in the expectation of finding more productive underlying sand, and a water-bearing stratum is tapped. In this case the problem is the reverse of the normal; water must be prevented from ascending rather than descending. A discussion of well-drilling methods is not within the scope of this paper, except such operations as pertain to shutting off of water. A brief outline of the several conditions which may accompany drilling follows. Some or all may be present in any particular case. The direct relation of these to prevention of intrusion will be discussed in detail further on. In drilling, the hole becomes more or less irregular in shape, and rough, and as the casing follows the bit into the well it does not fit snugly against the walls. As a result, water may descend between the casing and walls of the well. If a circulation pump is not used during drilling, the hole is simply punched through and the pulverized material removed from the well by means of a bailer. If circulation is maintained there is a continual flow of water down inside the casing and up around the outside between the pipe and the walls of hole. This keeps an open space around the pipe.

Jan 1, 1915

1. What Is a Rock Burst? . . . . 569 Jack Spalding . . 569 A. F. Robertson . 569 W. R. Crane . 569 G. S. Rice......569 P. J. Shenon........... 569 L. C. Graton........... 569 2. What Are the Causes of Rock Bursts? 573 Jack Spalding..........573 A. B. Yates and P. J. Shenon 574, 578, 592, 596 A. F. Robertson . . . . . 575, 595 W. R. Crane. ... 579 G. S. Rice.........582 Oscar Weiss .........582 P. B. Bucky..........582 P. H. Bird.....588, 592, 593, 595 M. K. Hubbert.........593 G. Wheeler.......... .593 B. F. Tillson........593, 595 T. T. Read............594 3. How Can Rock Bursts Be Prevented?. 597 Jack Spalding..........597 A. B. Yates and P. J. Shenon ... 598 A. F. Robertson.......599 W. R. Crane....... .602 G. S. Rice............602 Page 4. How Can Rock Bursts Be Predicted?. 602 Jack Spalding.........602 A. F. Robertson.......602, 603 A. B. Yates and P. J. Shenon ... 602 W. R. Crane......602 G. S. Rice......602 B. F. Tillson...........603 5. How Can Rock Bursts Be Controlled? 603 Jack Spalding..........603 A. F. Robertson.......603 W. R. Crane...........604 A. B. Yates and P. J. Shenon 604 Oscar Weiss........605 G. S. Rice......- 604, 609 R.D.Hoffman..609, 610 R. D. Hall..........609 R. H. Cromwell . . 609 P. J. Shenon...........609 P. B. Bucky......609, 611 B. F. Tillson.........609, 611 A. B. Yates...610, 611 P. H. Bird.......610 6. General Discussion........ 611 Jack Spalding.......... 611 R. D. Parker....... . 616 C. Baring Horwood........ 618 P. B. Bucky........... 619 Foreword This symposium brings together points of view, experiences and ideas on rock bursts from a goodly portion of the globe. Some conceptions, particularly those regarding the necessity of depth, have been fairly well shattered, as we find that they are present in the water tunnels of New York, on the surface at marble quarries in Vermont, and in the coal mines of the United States, as well as in the deep mines of the South African and Kolar gold fields, and in the nickel, copper and gold mines of Canada. Their occurrence under such a variety of conditions is, therefore, a challenge, which, if successfully met and overcome,

Jan 1, 1946

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif&apos;fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.&apos;-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.&apos; Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators&apos;&apos; recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.&apos;-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

[59H1-Water Law and Its Significance to the Mining Industry by Wells A Hutchins 59H2-Relation of Land Subsidence to Groundwater Withdrawals in the Upper Gulf Coast Region, Texas by Leonard A Wood and A G Winslow 59F3-Hydraulic Mining of Gilsonite and Its Application to Coal Mining by J H Baker 59H4-Recovery of Phosphates by In Situ Fluid Mining by Sylvain J Pirson 59F5-Coal Cleaning Plant Design for Minimum Operating Labor by Wm M Bertholf and John D Price 59F6-Coke Combustibility A Neglected Characteristic by J D Price 59B7-Union Carbide&apos;s Uranium Operation at Maybell, Colorado by K W Lentz and F T Temple 59H8-A Rapid Method for Estimating Alumina in Feldspathic Sands by Hugh H Bein 59H9-Water Laws as Related to Dredging in Idaho by Robert A Lothrop, Richard B Porter, and Robert P Porter 58B19-Separation and Washing of Alumina Process Residue by Morton Handelman 59B11-Feed Preparation and Froth Modification for Fatty Acid Flotation by Carl C Martin and Burt C Mariacher 59B12-Design Requirements for Tailing Disposal in the Southwest by E Vern Given 59B13-Semi-Dome Shaped Buildings for Bulk Storage by Edward E Ives and William L Payne]

Jan 1, 1961

NEW MEMBERS The following list comprises the names of those persons who became .members during the period of Jan. 10, 1918, to Feb. 10, 1918. ANTISELL, TONER, Min. Engr.; Supt., Great Falls Mine of Maryland, Chevy Chase, R: F. D. No. 4, Washington, D. C. BAKER, RAYMOND FRANK, Geol:, The Texas Co., Producing Dept., Box 362, Tulsa, Okla. BERTON, ADRIEN, Chief Engr., Corocoro United Copper Mines, Ltd., Corocoro, Bolivia. Buck, WILMER EARLE, Met., Curtis & Co. Mfg. Co., Hamberger & Kienlein Aves., St. Louis, Mo. BUELL, WILLIAM H., Asst. Director, Experimental Station, E. I. duPont de Nemours & Co., Wilmington, Del. CARDENAS, FEDERICO F., Mgr., Cia. Minera Nazareno y Alicante, S. A., Allende, No. 112, Saltillo, Coah., Mexico. CHEVALIER, JEROME A., Pet. Geol., The Carter Oil Co.; Exchange National Bank Bldg., Tulsa, Okla. CLEAVES, DANIEL LUNT Supt., St. Joseph Lead Co., Herculaneum, Mo. CLOTHIER, GEORGE A., Resident Min. Engr., Province of British Columbia,

Jan 3, 1918