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By J. R. Long, C. E. Armantrout, A. H. Roberson, T. R. Graham

The preparation and fabrication of copper-manganese-zinc alloys and the evaluation of their engineering properties have for some time been an integral part of a research program of the Federal Bureau of Mines. In this project, the use of electrolytic manganese, along with high purity copper and zinc, has permitted the preparation of alloys which contain a minimum of impurities which are capable of producing detectable effects in the properties studied. The initial work on the physical properties of wrought alpha solid solution alloys and a general outline of the alpha solid solution area for alloys containing up to 40 pct manganese have been presented in previous reports. 1,2,3,4,5 The evidence accumulated in these investigations clearly showed that additions of manganese to the copper-zinc alloys improve the strength properties of the brasses without seriously reducing their characteristic ductility and that considerable quantities of manganese could be added to the copper-zinc alloys without exceeding the mutual solubilities of manganese and zinc in copper. In continuation of these studies, additional data have been obtained in a more extensive investigation of the phase relationships of the copper-manganese-zinc ternary system. The present report delineates the solid phase boundaries of the ternary system from the copper-zinc binary to the manganese-zinc binary for alloys containing up to 50 pct zinc. Summary The alloys used in this investigation were conditioned by working schedules designed to homogenize the structures prior to heat treatments required for the equilibrium phase sludy. The treated alloys were examined by metallographic methods including hardness and X ray data for confirmation. The composite data of the investigation are summarily presented in a series of isothermal sections of the ternary system at 1100, 1200, 1300, 1200, and 1500°F. The salient features of the system as outlined by these data are: (1) the continuous alpha solid solution which extends across the diagram to the gamma-manganese phase of the manganese-zinc system at temperatures of 1200°F and higher, (2) the beta phase of the copper-zinc system similarly forms a continuous solid solution with its counterpart the beta field of the manganese-zinc binary, (3) at 1100°F (593°C) these alpha and beta fields are greatly restricted by complications arising from the allotropic transitions of manganese and the decreasing solubility of manganese in the alpha solid solution. The alpha + beta fields intersect the alpha + alpha manganese field to produce the beta + alpha manganese field and two adjacent three phase fields consisting of alpha + beta + alpha manganese and gamma + beta + alpha manganese. Typical microstructures representative of the various phase areas at each temperature are also presented. Review of Previous Work The copper-manganese-zinc alloys have periodically been the subject of numerous investigatioris of both prac-

Jan 1, 1950

By L. S. Richardson, N. J. Grant

Iodide-grade titanium, two oxygen alloys, and two aluminum alloys were studied by means of creep-rupture tests from 1000° to 2000°F. From the test information an evaluation was made of, 1) the relative creep-rupture strengths of the u (hexagonal-close-packed) and 0 (body-centered-cubic) forms of titanium and some of its alloys; 2) the effects of solid-solution strengthening by oxygen and aluminum on the u and 0 structures; and 3) the extent and effect of atmospheric oxygen alloying on rupture life in tests above about 1000°F. THE use of titanium alloys at temperatures above 1000° F has been considered unlikely by most investigators because of low creep strength (based on a requirement for room-temperature ductility, formability, and weldability) and low oxidation resistance. The results of this testing program do not entirely uphold this pessimism in terms of strength and oxidation resistance. The observations described below are based entirely on stress-rupture results, although some creep tests were also carried out on these alloys. Three items of primary importance are covered: 1) Stress-rupture data in the form of the Larson-Miller parameter curves for several titanium alloys at temperatures up to 2000°F; 2) The relative strengths of the hexagonal-close-packed a structure and the body-centered-cubic 0 structure; 3) The effects of solid-solution alloying on the creep-rupture properties of titaniu'm at elevated temperatures. Only two investigatons have reported the creep- rupture properties of titanium at temperatures above 1000° F. Lunsford and rant' tested iodide titanium; their values are also utilized in the paper. EXPERIMENTAL PROCEDURE After a few tests had been made in a conventional creep-rupture test machine, it became clear that some sort of atmospheric protection would be necessary for short-time tests conducted at temperatures above 1600°F, or for times greater than 100 hr at 1200°F or above. Several furnace units and test machines were constructed, the most successful of which is shown in Fig. 1. Certain experimental difficulties peculiar to titanium were encountered; for example, the use of molybdenum holders was dictated because titanium forms low melting-point eutectics with conventional high-temperature alloys containing appreciable amounts of iron, nickel, or cobalt. This same difficulty made the use of chrome l-alumel thermocouples in direct contact with a test specimen impossible, above about 1500" F. The high-temperature high-vacuum furnace shown in Fig. 1 was capable of maintaining a vacuum of better than 10"5 mm of mercury at 2000°F (pressure measured in cold part of system) and 5 X lo-' mm at room temperature. Most of the tests eonducted in vacuum were at temperatures

Jan 1, 1960

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

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

Jan 1, 1949

By W. W. Schmittroth, A. Y. Bethune

THE commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc .are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "superpurity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,1 it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon was not desirable. The use of Special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1946

By J. E. Burke

Recent investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers 1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen. Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: D = Ktm [,] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Wa1ker4 finds that, in alpha brass) the rate of growth falls off more rapidly than indicated by Eq i after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: ] where h and tz are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck3 The results obtained by Beck Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and HuV ater demonstrated expcrimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,io Making implicit use of this assumption, several authors14,16 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parkerg have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary7 are on the average more surromded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1949

By Glenn R. Zellars, J. P. Morris

The carrier gas method was used to measure the vapor pressure of copper over liquid copper and Fe-Cu alloys. From these results, the activity of copper in the alloys was determined at 146°, 1550°, and 1600°C. Calculations of the activity of iron were made from the results for copper. The activities of copper and iron show strong positive deviations from Raoult's law. KNOWLEDGE of vapor pressures of liquid metals has both practical and theoretical value. Fuming of metal baths is directly related to vapor pressure, and the data should bc particularly important to the technology of vacuum metallurgy. Theoretical applications include determinations of heats of vaporization, heats of solution, and activity coefficients in alloys. Methods for measuring vapor pressures of metals have been reviewed by Speiser and Spretnak.' High-vacuum procedures, such as the Langmuir and Knudsen methods, have been used most widely in recent years. However, these methods are not applicable to vapor pressures greater than lo-' mm Hg and often cannot be used in the temperature range of greatest interest. The purpose of this investigation was to develop a procedure for measuring vapor pressures of pure metals and alloys that would be applicable to pressures greater than lo-' mm Hg. The transportation or carrier gas method has been used. Copper was chosen for the initial work because its vapor pressure has been established fairly well and the reliability of the technique could be ascertained. Applicability to alloys was studied by determining the vapor pressure of copper over liquid Fe-Cu alloys. Experimental Procedure The tests were carried out in a graphite-spiral resistance furnace. The charge consisted of 50 g of metal contajned in a covered sintered-alumina crucible 1/2 in. deep and 13/8 in. ID. Two sintered-alumina tubes led from outside the furnace to within the crucible, passing through close-fitting holes in the crucible cover and radiation shield. The arrangement of the crucible and the two alumina tubes is shown in Fig. 1. The small-bore tube (1/16 in. ID by 5/16 in. OD) served as the inlet for the carrier gas. The tip of this tube touched the metal surface and the flow of gas imparted a rippling motion to the metal. In this manner the gas was brought into close contact with the metal and became saturated with metal vapor. In most of the tests the flow rate of the carrier gas was 560 ml per min, measured at room temperature. Approximately half of this saturated gas was allowed to escape from the crucible through the second alumina tube (3/16 in. ID by 5/16 in. OD) and was discharged to the atmosphere through a

Jan 1, 1957

By T&apos Ke, ing-sui

Accoriding to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on anelastic effects are important in many fields of metals technology. The, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.3 However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties Of meta1s in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies Of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often Can be Obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result Of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion,4-7 the stress-induced diffusion of particles,8-l2 and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we Can demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1949

By T&apos Ke, ing-sui

Accoriding to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on anelastic effects are important in many fields of metals technology. The, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.3 However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties Of meta1s in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies Of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often Can be Obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result Of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion,4-7 the stress-induced diffusion of particles,8-l2 and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we Can demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1949

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By Charles S. Barrett

THIS paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstructures. About 12m exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,1 and a number of these have been selected to illustrate the results obtained. Prints are also included showing the common types of falsities-to borrow a term from the biological field, the "artifacts." In brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. n addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains. Since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. SPECIMEN PREPARATION AND PHOTOGRAPHS Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for repeated polishing and etching (each successive polish becoming less severe and each etch lighter), since the final etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and IC, the replicas used were of silica, deposited up0n polystyrene and floated from the polystyrene in ethyl bromide according to polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1943

By J. A. Jaekel, W. C. Aitkenhead

Uranium deposits in the Spokane Indian Reservation, as well as those around Mt. Spokane, are essentially low grade, much of the ore containing less than 0.2 pct U3O8. The Mining Experiment Station of the Division of Industrial Research, State College of Washington, has been engaged in intensive research on the amenability of these low grade ores to froth flotation. The results: successful flotation of autinite, chief mineral constituent. At the outset of this work the goal was a concentrate of 1 pct U3O8 with a 90 pct recovery from ores containing less than 0.2 pct U3O8. Most of the work has been done on argillite ore from the Midnight mine on the Spokane Indian Reservation. The goal has not been attained using this ore, but samples of the granite ore from Mt. Spokane yielded successful results. For example, a concentrate containing 11.2 pcl U3O8 was produced from a Mt. Spokane high grade ore containing 1.27 pct U3O8 with a recovery of 97.8 pct. Another Mt. Spokane ore yielded a concentrate of 5.0 pct U3O8 from an ore containing 0.13 pct U3O8. with a recovery of 85 pct. This same ore gave a recovery of 93.5 pct when the grade of concentrate was reduced to 2.0 pct. It has been concluded that a successful method for floating autunite has been developed and that the mediocre results from the Midnight argillite ore are probably caused by the presence of some other uranium mineral or minerals less amenable to these reagents. The experimenters tested a third type of Washington ore, found on the Northwest Uranium Mines Inc. property on the Spokane Indian Reservation. This is a conglomerate of pebbles and small boulders of partially decomposed granite and is shot through with autunite. Its characteristics lie between those of the Midnight ore and the granite ore from the Spokane district. It responds better than the ore from Midnight but not as well as that from Mt. Spokane. As the fatty acids are the only type of collectors showing promise, investigation has been concerned with these acids and the optimum conditions for their use. The first method for treating the argillite ore from the Spokane Indian Reservation made use of Cyanamid's R-708 as a collector, a tall oil product described as a substitute for oleic acid. Although the investigators proved that R-708 is a collector for autunite when mixtures of autunite and silica sand are used, results on the ore were mediocre. Tests of other fatty acids revealed that the solid fatty acids of the saturated series are collectors for autunite and that their collecting power increases with the length of the carbon chain. The even carbon members of the whole series were tested from the 10 carbon acid (capric) to the 22 carbon acid (be-henic). The least expensive collector, stearic acid (18 carbon), proved to be a good one, so this was used in most of the tests. In first attempts with stearic acid, the collector was dissolved in various hydrocarbons and the solutions were added to the flotation cell. Cyclohexane, gasoline, fuel oil, kerosene, and other solvents were tried. Small amounts of high grade concentrates could be brought up, but recoveries were low. Finally emulsions of stearic acid were tried. It was discovered that stearic acid alone has little collecting power except when conditioning is carried out at high temperature. When hydrocarbon solvents were also present, it proved to be an excellent collector. An example of one emulsion that proved satisfactory for some ores is given as follows: 1 part stearic acid by weight, 1 part sodium oleate by weight, 1.2 parts kerosene by weight, 100 parts water. In some successful tests part of the stearic acid was replaced by oleic acid. The emulsions were made by agitating the stearic acid and sodium oleate together with hot water, then adding the kerosene and agitating while cooling. In the five tests reported in Table 1, 650 g of ore were ground with 650 cc water in a laboratory rod mill. The pulp was filtered to eliminate excess water and the ground ore transferred to a stainless steel beaker for conditioning at high pulp density. In most of the tests sodium hydroxide was added to the conditioner during agitation, then the collector emulsion, and finally the sodium silicate. The amount of alkali was adjusted to give a pH of 8.5 to 9.0 in the flotation cell. After conditioning the pulp was transferred to a laboratory flotation cell and the test completed in a normal manner. It is interesting to note that a deposit of high grade concentrate forms on the conditioning agitator and in the conditioning vessel, and at times on the agitator of the flotation cell itself. A few grams of concentrate running as high as 4 pct U3O8 were recovered from the conditioner when Midnight ore containing less than 0.2 pct U3O8 was treated. In the examples given in Table I this conditioner concentrate is calculated as part of the total concentrate. The authors have not yet fully explored the possi-

Jan 1, 1960

By C. E. Schwab

A lead-zinc orebody, in fairly strong quartzite and with a dip of 35" to 60°, is block-caved by use of scrams in a stair-step pattern up the ore footwall. Scram linings to handle coarse muck and permit the use of folding scrapers are developed by the use of end-grain wooden blocks to reduce maintenance and keep operating cost to a minimum. THE Bunker Hill mine, since its discovery in 1885, has steadily produced a high grade of lead-silver-zinc ore. By the end of 1952 over 21,000,000 tons of this high-grade ore had been produced by square-set mining, and reserves in the mine continue to be very satisfactory both as to quantity and grade. For many years prior to 1941, mine production and mill capacity had been 1200 tons of feed per day. Closely adjacent to the mill, and stored behind dikes, coarse jig tailings had been impounded during the time preceding the advent of fine grinding and selective flotation. When manpower became short in 1941 and sink-and-float preconcentration was proved successful, mill capacity was increased to 1800 tons per day to treat these jig tailings economically. By 1946, because the supply of jig tailings was limited, underground exploration was started to discover and prove ore reserves of low-grade material which could be mined by an appropriate bulk mining method. During the years of square-set mining many possible areas of low-grade mineralization had been observed. One chosen for the first exploration work was sufficiently remote from active mining areas so that subsidence, if an ore-body were proved, would cause no problem. Also, old adits and workings were still open and in good enough condition so that exploration in the mineralized zone could be started with a minimum of preparatory work. In 1948 an orebody was proved of sufficient tonnage, of a grade about 2 pct Zn, 0.5 oz Ag, and 1.0 pct Pb. It was decided to use block-caving, the only appropriate mining method by which this grade of ore could be economically recovered. Exploration for additional reserves in other areas of the mine is continuing, but ultimate results are not known at this time. With more sink-and-float capacity, larger ball mills, and more flotation machines, mill capacity was increased to 3000 tons per day, permitting the mining of ore in the square-set area at a maximum rate not usually achieved, because of the scarcity of labor. Increased mill capacity also permits block caving and the mining of jig tailings at variable rates to keep mill feed up to 3000 tons per day. Fortunately the three types of feed are amenable to the same mill circuit and reagents for recovery of Pb and Zn. For example, during the first 10 months of 1952 square sets produced 827 tons per day, block-caving 1421 tons per day, and jig tailings 643 tons per day, an average daily production of 2891 tons for all three products. Exploration had proved the existence of an ore-body 1000 ft long and 165 ft wide in horizontal section, see Fig. 1. Company engineers were concerned only with the vertical extension, about 300 ft, from an old level to the surface. Much of this almost outcropped, Fig. 2. The ore lies in the hanging wall of a major fault of the Bunker Hill mine, standing at 65" in one end of the zone and separated from the fault by a wedge of waste, see Fig. 3. This wedge pinches out near the center of the zone, at which point the ore dips 45", lying nearly on the fault, Fig. 4. The remaining portion lies on the fault and conforms to the fault dip of 35", Fig. 5. Open-pit mining for the top of the ore was considered, but since the ore zone dipped into and under the mountains, adverse waste-to-ore ratios precluded use of this method. The ore occurs in massive quartzite of sufficient strength to support untimbered drifts, crosscuts, and raises. Zones of weakness in the quartzite are bedding, jointing, and small faults or slips. The mineralization, which occurs as small stringers of sphalerite and galena as well as pyrite, creates another line of weakness. The mineral veins or veinlets in themselves are high-grade. Their size and regularity and the amount of barren quartzite by which they are separated determined the limits of mineable ore, which are all assay limits except for the one determined by the major fault. Block 1 Without any background of caving in this type of quartzite, engineers selected the first block on the very steep end of the zone. Compelling reasons prompted this decision. The steep portion of the ore in Block 1 was of the lowest grade, so that if difficulties were encountered no very valuable ore would be lost, while the experience gained might be applied in mining the remaining blocks. A block 200x200 ft was laid out, with four scrams spaced 50 ft apart for drawing and placed at a right angle to the strike. Finger raises were placed in a 25-ft interval grid pattern, with flat undercutting done by crosscuts at the undercut level 25 ft above

Jan 1, 1954

By J. R. Szedon, T. L. Chu, G. A. Gruber

Amorphous adherent filnzs of silicon dioxide have been deposited on silicon substrates by the oxidation of silane at temperatures ranging from 650 to 1050C. Various diluents (argon, nitrogen, hydrogen) were used to suppress the formation of SiO2 in the gas phase. Deposition rates of the oxide were determined over the temperature range in question as functions of' re-actant flow rates. Etch rate studies were used for a cursory comparison of structural properties of deposited and thermally grown oxides. From electrical evaluation of metal-insulator-silicon capacitors it was determined that the interface charge density of deposited films is similar go that of dry-oxygen-grown films in the 850° to 1050 C temperature range. Deposited films exhibit several ionic instability effects which differ in detail from those reported for thermal oxides. Stable passivating films of silicon nitride over deposited oxides appear to be practical for use in silicon planar device fabrication. Such films can be prepared under temperature conditions which have less effect on substrate impurity distributions than in the case of grown oxides. AMORPHOUS silicon dioxide (silica) is compatible with silicon in electrical properties and is the most widely used dielectric in silicon devices at present. Silica films can be prepared by the oxidation of silicon or deposited on silicon or other substrate surfaces by chemical reactions or vacuum techniques. The ability of thermally grown silicon dioxide films to passivate silicon surfaces forms one of the practical bases of the planar device technology. Properly produced and treated films of grown SiO 2 can have low densities of interface charge (-1 X 10" charges per sq cm) and can be stable as regards fast migrating ionic sgecies. 1 To maintain these properties, even with an otherwise hermetically sealed ambient, the Sia layers must be at least l000 A thick. Such thicknesses require oxidation in dry oxygen for periods of 7.8 hr at 900°C or 2 hr at 1000°C. Although oxidation in steam or wet oxygen can reduce these times to 17 and 5 min, the resulting oxides must be annealed to produce acceptable levels of interface charge., Oxidation or annealing involving moderate to high temperatures for extended periods of time can be undesirable. Under some conditions, there can be changes in the distribution of impurities within the underlying substrate. A chemical deposition technique using gaseous am-bients is particularly attractive and flexible for preparing oxide films. With a wide range of deposition rates available, films can be produced under condi- tions of time and temperature less detrimental to impurity distributions in the silicon than in the case of thermal oxidation. The pyrolysis of alkoxysilanes, the hydrolysis of silicon halides, and various modifications of these reactions are most commonly used for the deposition of silica films.3 Silica films obtained in this manner are likely to be contaminated by the by-products of the reaction, organic impurities, or hydrogen halides. The use of the oxidation of silane for the deposition process has been reported recently.4 The deposition of silica films on single-crystal silicon substrates by the oxidation of silane in a gas flow system has been studied in this work. The deposition variables studied were the crystallographic orientation of the substrate surface, the substrate temperature, and the nature of the diluent gas. The electrical charge behavior of Si-SiO2-A1 structures prepared under various conditions was investigated by capacitance-voltage (C-V) measurements of metal-insulator-semiconductor (MIS) capacitors. The experimental approaches and results are discussed in this paper. 1) DEPOSITION OF SILICA FILMS The overall reaction for the oxidation of silane is: The equilibrium constants of this reaction in the temperature range 500° to 1500°K, calculated from the JANAF thermochemical data,= are shown in Fig. 1. In addition to the large equilibrium constants, the oxidation of silane is also kinetically feasible at room temperature and above. However, the strong reactivity of silane toward oxygen tends to promote the nucleation of silica in the gas phase through homogeneous reactions, and the deposition of this silica on the substrate would yield nonadherent material. The formation of silica in the gas phase can be reduced by using low partial pressures of the reactants. Argon, hydrogen, and nitrogen were used as diluents in this work. 1.1) Experimental. The deposition of silica films by the oxidation of silane was carried out in a gas flow system using an apparatus shown schematically in Fig. 2. Appropriate flow meters and valves were used to control the flow of various reactants, i.e., argon, hydrogen, nitrogen, oxygen, and silane. Semiconductor-grade silane, argon of 99.999 pct minimum purity, oxygen of 99.95 pct minimum purity, and nitrogen of 99.997 pct minimum purity, all purchased from the Matheson Co., were used without further purification. In several instances, a silicon nitride film was deposited over the silica film. This was achieved by the nitridation of silane with ammonia using anhydrous ammonia of better than 99.99 pct purity supplied by the Matheson CO.' The reactant mixture of the desired composition was passed through a Millipore filter into a horizontal water-cooled fused silica tube of 55 mm

Jan 1, 1969

By R. F. Dickerson, D. A. Vaughan, A. F. Gerds

ALTHOUGH the metallurgy of uranium has been under intensive study since the early 1940's, no systematic effort has been made to identify the non-metallic inclusions in uranium. Uranium carbide (UC), which is probably the most common inclusion found in graphite-melted metal, has been tentatively identified by previous investigators, but the other nonmetallic inclusions have received little attention. Since metallography is a valuable tool in metallurgical studies, the metallographic identification of the nonmetallic inclusions in uranium is important. Such an investigation has been completed and the identification of slag-type inclusions and of uranium monocarbide, uranium hydride, uranium dioxide, uranium monoxide, and uranium mononitride is described. Metallographic Preporation It is often possible to prepare specimens for metal-lographic examination equally well by several methods. The specimens which were examined in this work were prepared by one of two acceptable methods. For the convenience of the reader, both methods will be discussed in detail and will be referred to simply as Method I or Method II in the subsequent sections. For both Methods I and 11, specimens for microscopic examination usually were mounted either in bakelite or in Paraplex room temperature mounting plastic. Method I—Specimens were ground in a spray of water on a revolving disk covered successively with 120-, 240-, and 600-grit silicon carbide papers. It was necessary to perform the final grinding operation carefully on worn 600-grit paper to keep the scratches as fine as possible. After washing and drying, the specimens were polished for 3 to 4 min on a slow speed wheel (250 rpm) covered with a medium nap cloth. Diamet Hyprez Blue diamond polishing paste, Grade 00, 0 to 2 µ, was used as abrasive with kerosene as lubricant on the wheel. Specimens were washed thoroughly in alcohol and final polished electrolytically in an electrolyte composed of 1 part stock solution (118 g CrO, dissolved in 100 cm3 H2O) with 4 parts of glacial acetic acid. A stainless steel cathode was used. At an open circuit potential of 40 v dc, a polishing time of 2 sec retained inclusions well with the bath at room temperature. If additional etching was required to sharpen the interface between the metal and the inclusions, an electrolyte composed of 1 part stock solution (100 g CrO3 and 100 cm8 H20) and 18 parts glacial acetic acid was used at room temperature. Best results were obtained by etching for from 10 to 15 sec at 20 v dc in the open circuit. Surfaces obtained by this method are suitable for microscopic examination. However, if desired, they may be etched further with other chemicals. Method 11—Rough grinding was done on a wet 180- or 240-grit continuous grinding belt. The specimen was then ground by hand successively on 240-, 400-, and 600-grit silicon carbide papers in a stream of water. Final polishing was accomplished on a 4 in. high speed wheel (3400 rpm) covered with Forstmann's cloth. Linde B levigated alumina, suspended in a 1 volume pet chromic acid solution, was the abrasive. Specimens usually were polished in 5 min or less by this technique. Often the inclusions present in the metal were identified in the mechanically polished condition. When etching was required to outline inclusions more sharply, one of the two following methods was used. In the first method, the specimen is etched lightly while electropolishing in the chromic-acetic acid solution described above (1 part of stock solution to 4 parts of acetic acid). The electrolyte was refrigerated in a dry ice-ethyl alcohol bath and specimens were etched at 60 v dc on the open circuit for 2 or 3 cycles of 3 to 4 sec each. The second technique utilizes electrolytical etching at about 10 v dc (open circuit) in a 10 pet citric acid solution at room temperature. X-Ray Diffraction Technique The major problem in the identification of inclusions in metals by X-ray diffraction techniques is the extraction of a sufficient amount of each type of inclusion to obtain an X-ray diffraction pattern. In the present study, X-ray diffraction patterns were obtained from individual inclusions of the order of 10 µ diam. The polished and etched samples shown in the micrographs were examined at a magnification of X54 or XI00 with a binocular microscope. This allowed sufficient working distance to extract the inclusions with a needle probe for powder X-ray diffraction analysis. Friable inclusions such as MgF2, CaF2, UO2, and UH3 could be freed from the metal by probing the as-polished and etched surface. The fine particles then were picked up on the end of a Vistanex-coated glass rod (0.002 in. diam) which was held in a brass adapter made to fit the powder X-ray diffraction camera. The end of the glass rod was centered in the path of the X-ray beam. In the case of the UC, UO, and UN inclusions which are smaller in size, more metallic in appearance, and less friable than the other inclusions, it was necessary to etch the inclusion in relief before extraction. UN inclusions etched sufficiently in relief in the electrolytic polishing solution described in Methods I and II by increasing the polishing time. UN inclusions were relief etched by extending the

Jan 1, 1957

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1' of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967

By J. Sibakin, R. D. Hindson

In order to devise a practicable soaking pit schedule for use at The Steel Co. of Canada Ltd.'s Hamilton Works, soaking pit heating temperatures, sooking times, pit capacity, and safe maximum mill drafts were correlated with fluctuations in the current or load of the bloom mill driving motor. Other variables such as total delays in the pit, rolling schedules, mill delays, and track times were also investigated. IN order to show an easily applied and accurate means of establishing soaking pit heating temperatures, soaking times, pit capacity, and safe maximum mill drafts, these various factors are correlated herein with fluctuations in the current or load of the bloom mill driving motor. Rolling practices have a considerable influence on the production capacity of a blooming mill. The maximum values of the torque, in particular, are of importance, since even instantaneous current peaks lead to the tripping of the motor by the overload relay and result in loss of mill time. The establishment of safe maximum drafts and accelerations for ingots of different sizes and of a soaking pit practice which would ensure a consistent and satisfactory plasticity of the metal is of considerable importance for increasing the efficiency of both the blooming mill and the soaking pits. The Bloom Mill Dept. of the Hamilton Works, The Steel Co. of Canada Ltd., is equipped with one 44 in. mill driven by a 7000 hp motor with the setting of the overload relay at 22.0 ka. The speed of rotation of the motor is regulated after the Ward-Leonard system. There are three basic speeds of 9.5, 28, and 47 rpm and a further possibility of increasing the speed by weakening the field. This last possibility is hardly ever used during practical operations. The rolling program of the blooming mill is varied, both in the size of the ingots to be handled and in the steel grades. The total tonnage handled by the mill is about 2,000,000 ingot tons per year. At the time of the investigation, the Bloom Mill Dept. was equipped with 22 soaking pits (6 regenerative, 14 bottom-fired, and 2 one-way top-fired pits) with a total bottom area of 2770 sq ft. The pits are fired with a blast furnace-coke oven gas mixture having a calorific value of 155 Btu per cu ft. The foregoing figures show that the production program was such as to impose the necessity of a most efficient usage of the available equipment. For this purpose, the operations of the 44 in. mill and of the soaking pits were investigated, and the results of the investigation were used as a basis for a revised soaking pit schedule and drafting practice. The plasticity of an ingot of a certain chemical composition when being rolled is determined mainly by the following factors: I—the ingot size, both thickness and width; 2—the length of the gas soak; and 3—the surface temperature. The first two factors determine the uniformity of the temperature distribution over the cross-section of an ingot. The third factor introduces the level of the heating of an ingot. The torque produced by an ingot being rolled is determined by the area of the metal displaced, its plasticity, and acceleration values. On the other hand, with shunt motors the torque is determined by the current. This can be assumed to be correct with only a small degree of error for compound motors with a relatively small effect of the series windings as long as the velocity is not regulated by weakening the field. Since the spread is relatively unimportant when compared to the width of an ingot and since it is also reduced several times during rolling by edging passes, the draft alone and not the area of the metal displaced may be taken into consideration with ingots of a similar size. It is therefore possible to determine the main features of the heating and drafting of an ingot by measuring the current and acceleration of the mill motor. After the acceleration has been taken into account, the amount of current will be an indication of how the motor responds to a heating and/or drafting practice and these practices can be adjusted in order to get the desired result. As peak currents are more likely when heavier ingots are rolled, the rolling of plate and slab ingots was investigated. Conditions prevailing when smaller ingots are rolled can be deduced from the results obtained on heavier ingots. All measurements were made when plain carbon grades under 0.15 pct C were rolled. The motor current, the voltage across the armature, and the rpm were recorded simultaneously on synchronized charts, Fig. 1, which moved with the speed of 6 in. per min. Each draft was recorded by a special observer. The rpm curve made it possible to establish the acceleration at any given moment. For purposes of correlation, the maximum current during a pass and the corresponding acceleration were used. The charts made it possible to establish the position of the roller's lever at any given moment as well as the total time of a pass. The slab ingots were divided into three groups (28x35, 28x45, and 27Mx53 in. ingots) and each group was investigated separately. Since they account for most of the current peaks, only flat passes were used for purposes of correlation, a total of 1373 having been investigated.

Jan 1, 1956

By William D. Klopp, Joseph R. Stephens

A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the &apos;<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over

Jan 1, 1969