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By Chas. H. Behre, Arbiter. Nathaniel

Two outstanding factors characterize most undertakings in the mineral industries: (1) mineral deposits are not equally distributed over the earth but are localized by natural processes, and (2) the mineral industries are largely based upon wasting assets. Neither of these factors is invariably true, for a few mineral materials, such as water, are essentially world-wide and others are replaced periodically by processes not unlike crop production. Indeed, with some, such as the salts in the sea, the supply is cyclic in short or long periods, whereas others, like water, though locally or periodically in short supply, are essentially inexhaustible. But to the extent that most minerals are limited to certain areas and are "permanently" consumed, any industry founded upon them, by implication, demands great care in planning for the most effective extraction-the essence of wise and conservative expenditure. Several less unusual yet also truly fundamental factors in the economics of the mineral industry are those involving (1) the various kinds and properties of mineral materials, which influence their use; (2) their geo- logic and geographic availability; and (3) the techniques unique to their discovery, exploration, and utilization. This chapter is designed primarily as a brief background for later ones and as a summary of the several un- usual or at least special factors and of their effect upon the economics of the mineral industry. The social and political and especially the economic aspects of the industry are the main subjects of this volume and are dealt with in extended fashion in subsequent chapters. Fundamental Characteristics of Mineral Deposits DEFINITIONS Minerals are naturally occurring compounds of nonliving matter, each technically defined as having (1) a chemical composition that may vary

Jan 1, 1959

By Enrique Touceda

For a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At the outbreak of the war the firm decided to specialize in the manufacture of propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods of manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual blade mold formed, the pattern is then rotated on the spindle to the position for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this pratctice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface of each blade must be chipped to the templet and through this procedure chipped to such accuracy as will be required for a static balance. Inasmuch as the work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin of the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days of foundry work and about the same length of time for the machining. Through the use of the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity with any particular propeller-wheel design.

Jan 1, 1922

By Enrique Touceda

For a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At the outbreak of the war the firm decided to specialize in the manufacture of propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods of manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual blade mold formed, the pattern is then rotated on the spindle to the position for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this pratctice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface of each blade must be chipped to the templet and through this procedure chipped to such accuracy as will be required for a static balance. Inasmuch as the work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin of the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days of foundry work and about the same length of time for the machining. Through the use of the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity with any particular propeller-wheel design.

Jan 1, 1922

By W. H. Andrews

THE constantly increasing consumption of Portland cement in the State makes the above subject of partlcular interest at this time. The increasing demand is due to the rapid settling of the country and the fact that new uses are being found frequently for the above named commercial article. The industry is one that is bound to grow as the population increases, and this being the case, it may be well ,it this time to consider briefly- the matter of the chemical and physical com-position of proper raw materials. A cement mixture is one that contains approximately 75 per cent. carbonate of lime, 15 per cent. Silica, and 5 to 7 per cent. alumina, and iron oxides; the other elements being magnesium carbonate and small quantities of the rarer elements general associated with limestone deposits. It call be readily seen from the above composition that it is possible to build up this mixture from a number of different materials. First.-A rock high in carbonate of lime can be mixed with clay or shale in such proportions as to bring about the desired composition ; the chief difficulty in the building up of such a mixture is that it is hard to find a clay or shale in which the silica-alumina, ratio lies .between 4 to 1 and 3 to 1 and at the same time shows physical characteristics which will make certain its adaptability to the practical manufacture of Portland cement. Very often clays or shales are found which are right chemically but contain large quantities of grit or free silica. Such clays or shale must be ground to extreme fineness in the mixture in order to make the silica and alumina combine with the lime when the mixture is burned. On the other hand, clays or shales are often found that have the proper physical characteristics but in which the amount of alumina, is too great.

Jan 9, 1913

By John J. Egan, A. B. Kinzel, Walter Crafts

The demands of the petroleum and chemical industries for steels to be used in pressure vessels and similar structures at artificially low temperatures are continually increasing, and the writing of proper specifications with suitable tests becomes increasingly important. Likewise, the selection of suitable steels for such applications is of increasing concern to the metallurgist. It is generally recognized that highly alloyed steels of the austenitic stainless type retain their properties even at very low temperatures and represent the best technological solution of the low-temperature steel problem. However, in many instances less expensive carbon or low-alloy steels suitable for service within limited temperature ranges are available. The problem thus becomes one of defining the various factors involved in the production and fabrication of these less expensive steels and determining the temperature ranges in which their properties justify engineering application. Most of the applications involve welded structures, and the heat effect of welding as well as the nature of the weld metal are matters of prime concern. The first problem that the metallurgist faces is the determination of the type of test to be used as a criterion of the performance of the steel in low-temperature service. It has been generally recognized that the static properties of steel as determined in the ordinary tensile test undergo a gradual and relatively slight change as the temperature of test is lowered in the range of current interest; i.e., from room temperature to minus 120' C. It is further generally recognized that the behavior of steel under impact involving notch sensitivity is definitely affected at the lower temperatures. While the major subject of this paper is the effect of grain-refining deoxidizers, of low-alloy additions and of welding on the low-temperature notched-bar impact properties, an inquiry into the general behavior of steel under low-temperature impact testing is included. This is a pertinent portion of the investigation and the results thereof are

Jan 1, 1937

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By H. E. Hostetter

Grossmann's method1 for calculating the hardenability of steel from the composition and grain size has gained wide acceptance, and when properly used, has been well proved in practical application, both for estimating the hardenability of known compositions and for selecting compositions to meet known hardenability requirements. The Grossmann method uses as the criterion of hardenadility the "ideal critical diameter," DI, which is the' size round that will just harden to a structure of 50 per cent martensite at the center when given the theoretically fastest quench, or "ideal quench." The DI can be related to actual quenching practice if the severity of quench is known; or the DI can be correlated with hardenability as determined by the Jominy end-quench method.2 The effect on hardenability of each element present in a steel can be represented by a multiplying factor, the value of which depends on the amount of the element present and the degree of effectiveness of the particular element. (The value of the factor for a given carbon content varies with the grain size.) When the factors for all elements present in a steel have been determined from charts, they are multiplied, and the resultant product is the DI of the steel. The validity of Grossmann's scheme of multiplying factors has been confirmed in a number of other investigations.3-6 It can be appreciated that a certain desired level of hardenability can be obtained by adding chromium, molybdenum, nickel and vanadium to a base composition containing carbon, manganese, silicon and the usual impurities. Many of the ranges of hardenability used commercially can be obtained by any of the foregoing alloying elements used singly in the base composition. The same hardenability levels also can be obtained through use of any of a great number of multiple element combinations of these alloying elements. In this report a method will be presented for determining what one combination is the most efficient (based on hardenability and cost of added alloy) for a given level of hardenability. It should not be assumed from the emphasis given to hardenability, that hardenability is the only criterion for the selection of an alloy composition. Such properties as the hot-working characteristics, machinability, carburizing characteristics, amount of distortion during quenching and the retention of austenite may be considerations of importance in many applications. However, hardenability is one of the most important properties of an alloy steel and one that must be considered in almost all cases involving heat-treatment by quenching. Therefore, a method for determining the lowest-cost alloy combination should be of considerable value. Determination of Most Efficient Combinations For comparing the alloying elements on standards of cost and hardenability, it

Jan 1, 1947

By H. E. Hostetter

Grossmann's method1 for calculating the hardenability of steel from the composition and grain size has gained wide acceptance, and when properly used, has been well proved in practical application, both for estimating the hardenability of known compositions and for selecting compositions to meet known hardenability requirements. The Grossmann method uses as the criterion of hardenadility the "ideal critical diameter," DI, which is the' size round that will just harden to a structure of 50 per cent martensite at the center when given the theoretically fastest quench, or "ideal quench." The DI can be related to actual quenching practice if the severity of quench is known; or the DI can be correlated with hardenability as determined by the Jominy end-quench method.2 The effect on hardenability of each element present in a steel can be represented by a multiplying factor, the value of which depends on the amount of the element present and the degree of effectiveness of the particular element. (The value of the factor for a given carbon content varies with the grain size.) When the factors for all elements present in a steel have been determined from charts, they are multiplied, and the resultant product is the DI of the steel. The validity of Grossmann's scheme of multiplying factors has been confirmed in a number of other investigations.3-6 It can be appreciated that a certain desired level of hardenability can be obtained by adding chromium, molybdenum, nickel and vanadium to a base composition containing carbon, manganese, silicon and the usual impurities. Many of the ranges of hardenability used commercially can be obtained by any of the foregoing alloying elements used singly in the base composition. The same hardenability levels also can be obtained through use of any of a great number of multiple element combinations of these alloying elements. In this report a method will be presented for determining what one combination is the most efficient (based on hardenability and cost of added alloy) for a given level of hardenability. It should not be assumed from the emphasis given to hardenability, that hardenability is the only criterion for the selection of an alloy composition. Such properties as the hot-working characteristics, machinability, carburizing characteristics, amount of distortion during quenching and the retention of austenite may be considerations of importance in many applications. However, hardenability is one of the most important properties of an alloy steel and one that must be considered in almost all cases involving heat-treatment by quenching. Therefore, a method for determining the lowest-cost alloy combination should be of considerable value. Determination of Most Efficient Combinations For comparing the alloying elements on standards of cost and hardenability, it

Jan 1, 1947

By T. R. Cass

THE renewed interest in titanium, resulting from its increasing application as a structural material, has stimulated basic deformation studies on this metal. In the course of our work, we have developed a dislocation etchant and applied it to a perfection study of melt-grown single crystals as well as to a preliminary investigation of plastic deformation in titanium. The etchant, Keller's etch (21 cu cm HF, 64 cu cm HC1, 106 cu cm HNO3, and 160 cu cm H20), reveals the emergence of both grown-in and fresh dislocations on pure titanium and a-phase Ti-Al single crystals. Pits are produced only on surfaces within a few degrees of the basal plane; the more exactly parallel to a basal plane the surface is, the more distinct are the pits. The observed pit density, however, does not appear to depend on the surface orientation; the pits simul- taneously become less distinct as the misorientation from a basal plane increases. Etch times are short, a few seconds, for pure titanium; longer times are necessary for alloy crystals.

Jan 1, 1968

By G. F. Jenkins

ASBESTOS is a general term embracing the fibrous varieties of a number of minerals. Of these, the hydrous magnesium silicate, chrysotile (H4Mg3Si209), a variety of serpentine, is the most abundant and useful to industry. All other types of asbestos belong to the amphibole group of minerals and are classified as: crocidolite, NaFe(SiO3), FeSiO3; anthophyllite, (MgFe)SiO3; amosite, also a ferromagnesium silicate but with iron content higher than that of anthophyllite; tremolite, CaMg3(SiO3)4; and, actinolite, Ca (MgFe)3(SiO3)4. PROPERTIES The commercial value of asbestos depends largely on the physical property that permits it to be readily separated into fine filaments of high tensile strength and flexibility, which, coupled with the fact that it has the quality of incombustibility of a mineral-in distinction to vegetable and animal fibers-makes it of unique usefulness for many purposes. To some extent, the value depends upon the length of the fiber, although extreme length is neither necessary nor desirable for most purposes. Chrysotile occurs as cross-fiber veins, in which the asbestos fibers are approximately' at right angles to the vein walls, with vein width- or fiber length-seldom exceeding 2 or 3 in.; also as slip-fiber, in which the fibers 'lie in the same plane as the vein or on slippage planes. A cleanly broken vein of cross-fiber has a pearly luster and may range from a deep green or brown color to light shades of yellowish green or cream. When of good quality, the fiber filaments forming the vein may be easily drawn away from their neighbors and exhibit a fine silkiness and pure white color. They may be twisted into a thread and when flexed between thumb and fingers are found to be strong and pliable. Chrysotile withstands comparatively high temperatures without breaking down completely or fusing but begins to lose water of crystalliza-

Jan 1, 1949

By AIME AIME

Air transport supplants the old methods. The 3-piece canoe fits in the plane and likewise makes possible not a bad division of labor over a 5-mile portage

Jan 1, 1933

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By H. D. Newell

THERE has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-tem-perature steels" are meant those specifically designed for service at ele-vated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service.

Jan 1, 1937

By Bunting S. Crocker

Bunting S. Crocker (Executive Vice President, Kilborn Engineering Ltd., Toronto, Ont., Canada)-This is an interesting report on laboratory-scale testing with pebble charges in 12-in.-diam mills, and the author correctly concludes that useful laboratory testing can be done. In the opening paragraphs he states, "laboratory pebble-milling tests have been considered too difficult to perform and not relevant enough to the actual grinding situation"!! This is definitely not so! The writer published detailed tests done in a 12-in.-diam mill comparing pebble and steel balls in 1952 6 and again in 1954 7. We note that our review paper in 1963 was the only one mentioned in the References. The author states that "a smooth lining is more frequently used in commercial-scale pebble grinding." The writer has designed some 22 plants treating 134,000 tpd in North America and Australia. He has also visited pebble installations in Norway, Sweden, Finland, and South Africa. All these plants correctly use heavier lifters than would be considered standard for ball mills of a similar size. Smooth liners are not recommended in wet ore treating plants. In the 1952 paper6 it was clearly demonstrated in the test work that the individual ore pebbles had to be the same weight-not the same diameter or size-as the steel balls if comparable grinding results were to be obtained. In the tests performed in this study most of the pebbles "passed 50-mm round hole screen openings and remained on a 40-mm round hole sieve. Correspondingly most of the ball mill experiments were performed with 50 or 40-mm steel balls". Thus, the balls and pebbles were essentially the same size or diameter. This means we are comparing apples and oranges. When the feed being ground is fine enough the pebbles will be superior. When the feed is coarse the steel balls will be the better. This is similar to grinding tests in which two sizes of steel balls are compared. In the middle of the article, "Crocker5 has reported that equal weights of pebbles and steel balls achieve the same grinding capacities under similar conditions …", then he proceeds to question this postulate. In the eight reports that I have published, I have never made this statement. What I have said is "for comparable grinding, the individual pebbles in the mill charge should be the same weight as the individual steel balls." This is not the first time that I have been misquoted on this point! It is most unfortunate that this test work has been done with a ball and pebble of the same diameter and not the same weight. It is impossible to properly evaluate the results. I also regret the fact that the screen analyses of the tests were not shown. Many of us who have been 40 years or less in the grinding game can easily read screen analyses at a glance. We can tell whether the top meshes are being ground by the ball charge, etc., etc. The graphs are fine for the summary or to illustrate conclusions but are often misleading in the report itself. However, we do agree that useful pebble grinding tests can be done in a 12-in. mill.

Jan 1, 1973

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By C. R. Swarts

The use of compressed air or gas in oil wells for raising crude oil to the surface has, within the last year, become a dominant factor In production engineering. Previous application of this principle was largely confined to oil wells that had been pumping for a considerable length of time. In the Seminole area, the gas-air lift has been applied to wells imniediately after natural flow has ceased and in some cases while the wells were still flowing. This early application of the gas-air lift has been watchcd with intense interest by the petroleum industry, both with respect to methods of application and mechanical installations and to the effects on immediate and ultimate production. Methods of Application The Seminole pool at its inception contained sufficient gas associated with the oil to cause natural flow. As no frce gas was found in the main productive horizon, the Wilcox sand, all the gas present was dissolved in the oil, hence the natural flowing life was short, rarely lasting over 45 days. When natural flow ceased, high fluid levels were common, and as depth and crookedness of holes were obstacles to efficient pumping, the gas-air lift was used almost exclusively in raising the oil to the surface. Because of the high gravity of the oil, 41" A. P. I., and its high gasoline content, and also because of the desire to obtain production before offset wells became productive, quantity of production was the aim of the operators and a method of flow was used whereby this aim could be fulfilled. One of the outstanding features of this method consisted in flowing the wells through the annular space between the tubing and rasing. By this means a greater quantity of fluid could be handled than by flowing through the tubing of the size in ordinary use. Wells that would produce only a few hundred barrels on the pump were by this rnethod made to produce as high as 7000 bbl. on the lift. A few days or wreks of production at that rate meant a large recovery of oil. Casing of 636 in. diameter was commonly used as a production string with a 5 3/16-in. liner set on top of the oil sand. Upset tubing for irtro-

Jan 1, 1928