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By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

By F. I. Grace, L. E. Murr

The mechanical responses and residual defect structures in 70/30 brass and type 304 stainless steel following explosive shock loading and cold reduction by rolling have been studied. A distinct relationship was observed to exist between the residual mechanical properties and micro structures observed by transmission electron microscopy. Shock-loaded brass deformed primarily by the formation of coplanar arrays of dislocations and stacking faults at lower pressures, and twin-faults (deformation twins and €-martensite bundles) at higher pressures (> 200 kbar). The micro -structures of cold-rolled brass were characterized by dense dislocation fields elongated in the rolling direction. Stainless steel was observed to deform by the formation of dense arrays of stacking faults at lower shock pressures and twin-faults at high shock pressures (>200 kbar). Lightly cold-rolled stainless steel deformed similar to low Pressure shock-loaded stainless steel, but transformed to a' martensite in heavily cold-rolled stainless steel. Discontinuous yielding was observed for the heavily cold-rolled stainless steel, and stress reluxution in the weyield region for cold-rolled and shock -loaded stainless steel was interpreted as an indication of the ability of twin-faults and stacking faults to act as effective barriers to dislocation motion. A simple model for the formation of the planar defects and a' martetnsite is presented based on the propagating of Shochley partial and half-partial dislocations. A considerable effort has been expended over the past decade in an attempt to elucidate the response of metallic-crystalline solids to the passage of a high velocity shock wave (e.g., smith,' Dieter,2 and zukas3). While it has been possible to obtain relevant information pertaining to the residual defect structures and mechanical properties, there have been few rigorous attempts to draw a direct comparison between these structures and properties. In addition, numerous investigators have recently observed the occurrence of deformation twinning in shock deformed fcc metals (e.g., Nolder and Thomas,4 and Johari and Thomas5), but little attempt has been made to elucidate the mechanisms of formation of these defects. Comparative data for metals deformed by shock-loading and the same metals deformed by more conventional modes of deformation such as cold-reduction by rolling is also generally lacking. The present investigation therefore has the following objectives: 1) to examine the mechanical properties of some explosively shock loaded and cold-rolled fcc metals of low stacking-fault energy as a function of their residual substructures; 2) to present a simple model for the formation twin-faults and related defect structures in the low stack-ing-fault energy materials of interest (70/30 brass, ySFg= 14 ergs per sq cm; and 304 stainless steel, ySF = 21 ergs per sq cm); 3) to make some deductions with regard to the residual characteristics of dislocation and planar defect substructures in cold rolled and shock loaded 70/30 brass and type 304 stainless steel. In particular, it was desirable to characterize the residual hardening effects of particular deformation substructures. I) EXPERIMENTAL PROCEDURE Sheet samples of 70/30 brass (0.005 and 0.15 in. thick; annealed at 659°C for 2 hr) and type 304 stainless steel (0.007 in. thick; annealed 0.25 hr at 1060°C) of nominal compositions shown in Table I were cold-rolled in one direction only to produce reductions in thickness of 15, 30, 45, 60, and 75 pct in the brass; and 5, 15, 25, 35, and 45 pct in the stainless steel. Identical sheet samples in the annealed (unrolled) state were subjected to plane compressive shock waves to various peak pressures ranging from 0 to 400 kbar in the brass and 0 to 425 kbar in the stainless steel; and with a constant peak pressure duration of approximately 2 microseconds. A detailed description of the shock loading technique has been given previously.6 Tensile specimens 1.0 in. in length and 0.125 in. in width were cut from the cold-rolled sheets (tensile axis parallel to the rolling direction), and the shock-loaded sheet specimens. Stress (load)-strain (elongation) measurements on the tensile specimens were made on a Tinius-Olsen load-compensating tensile tester using a strain rate of 2.7 x 10-3 sec-1. Tensile tests were repeated at least twice, giving essentially the same results. Stress relaxation measurements in the preyield region were also made using an initial strain rate of 5.4 x 10-4 sec-1. In addition to tensile and stress relaxation measurements, Vickers microhardness measurements were made on all samples. A total of 100 microhard-ness readings were obtained for each specimen following a light electropolish to ensure uniform surface conditions for all tests. The hardness averages ob-

Jan 1, 1970

By Carmine D. &apos, Lemuel Tarshis, Joel Hirschhorn, Antonio

Vapor-deposited nickel films in the thickness range 700 to 4360A were tested in uniaxial tension utilizing a microtester designed specifically for this study. Contrary to the findings of some investigators, a definite thickness-strength relationship was observed below 3000 A with a four-to sevenfold increase in strength over that of bulk nickel. The films were characterized by high elastic strains and little plasticity. On the basis of these and other reported data, it is suggested that the high strength level in metal films is related to the manner in which they are produced. Vapor deposition, owing to its severe quenching effect. is believed to promote the formation of point defects which inhibit dislocation movement. IN recent years it has been reported that metals, when in the form of thin films, exhibit extraordinarily high strengths. The data published to date have been primarily concerned with silver and gold because of the ease with which these metals can be vapor-deposited and their high resistance to surface oxidation. Previous investigations into the mechanical strength of thin films has uncovered an apparent dichotomy of view on film behavior. Beams and his co-workers have reported a definite dependence of strength on film thickness. Other workers,"-'6 however, in separate studies on the strength of poly crystalline and single-crystal films have found no such thickness-strength relationship. The study of thin-film strength is extremely difficult because of the many variables associated with film preparation, handling, and testing. Moreover, the manner of test employed by different investigators has varied quite radically, ranging from simple uniaxial-tension to biaxial-bulge testing. The work reported herein was conducted in order to determine the mechanical behavior of a structural metal when in the form of a vacuum-deposited thin film and to gain some insight into the reasons for the high strengths exhibited by metals having such a con- figuration. In this study a method of test was chosen which would yield results which are easily interpreted and lend themselves to comparison with properties of the same material in bulk form. Moreover, specimen-preparation parameters and film-handling techniques are set forth so that other investigators can properly compare their findings with ours. EXPERIMENTAL PROCEDURES A) Film Preparation. Vacuum deposition was performed in an 18 by 30 in. bell jar using a standard New York Air Brake Co. vacuum station with a 6-in. oil-diffusion pump. Before evaporation the system was pumped to a pressure of less than 2 x 10"5 torr. A shield was employed to protect the substrates from the emission of contaminants during the critical melting and outgassing of the evaporant. The source consisted of from one to six filaments (0.020 in. diam). The length of each filament was about 5 in. and was placed 6 to 8 1/2 in. from the substrate in such a manner that the substrate face was at 90 deg incidence with respect to the evaporant beam. The temperature of the source was 2000"~ during evaporation. The films were deposited onto a substrate arrangement which was composed of four basic components, that is: 1) a 3 by 1 in. glass slide; 2) a 22-mm sq micro cover glass on 1); 3) a 22 by 50 mm micro cover glass coated with collodion on 1); and 4) a stainless-steel sheet mask containing twelve rectangular openings of 1-mm and 2-mm widths and lengths of 5 mm laid over 3). Thus, test specimens of 1-mm and 2-mm widths are deposited onto a collodion substrate which precludes epitaxial effects in the specirnens. 17-le The rectangular cover glass and square cover glass were positioned in such a manner that a strip of film would be evaporated along the length and across the width of the large glass slide. This boundary of evaporated film was used to determine the film thickness by multiple-beam interferometry. The square cover glass was used for X-ray and chemical analyses. Thickness of the deposits was varied by changing the number of filaments used (one to six). The duration of evaporation was 30 sec for each filamgnt which resulted in a deposition rate of 8 to 20A per sec. Evaporations were all performed at room temperature; however, radiant heat from the source raised the substrate temperature to 40" to 60°C. All substrates were cleaned by ultrasonic agitation in a solution of spectranalyzed isopropyl alcohol. Collodion was deposited on the micro cover glass by immersion in solution of collodion in amyl acetate. B) Thickness Control and Measurement. Film

Jan 1, 1963

By George S. Ansell, Thomas E. Davidson

It has been known for a considerable period of time that the ductility of even quite brittle materials can be enhanced if they are deformed under a superposed hydrostatic pressure of sufficient magnitude. The response of ductility to pressure, however, has been shown to vary considerably between materials. Prior work has shown that the effects of pressure upon the tensile ductility of Fe-C materials depend upon the amount, shape and distribution of the brittle cementite phase. In this current investigation, the effects of pressure upon the fracture mechanisms in a series of annealed and spheroidized Fe-C materials were examined. It was observed that the principal effect of pressure is to suppress void growth and coalescence, retard cleavage fracture and to enhance the ductility of cementite platelets in pearlite. Based upon the observed effects of pressure upon the fracture mechanisms, a proposed explanation for the enhancement in ductility by pressure and for the structure sensitivity of the phenomena is presented and discussed. THE effect of superposed pressure upon the tensile ductility of a variety of metals has been well documented.'-'' Some of the results from several investigators are summarized in Fig. 1 where tensile ductility in terms of true strain to fracture (ef) is plotted as a function of the superposed pressure. As can be seen, a pressure of sufficient magnitude can significantly enhance the ductility of metals. However, Fig. 1 also demonstrates that the response of ductility to pressure and the form of the ductility-pressure relationship varies considerably between materials. Several explanations have been offered for the observed enhancement in ductility by a superposed pressure. Although no experimental evidence was provided, Bridgman13 and Bobrowsky10 proposed that the observed effect was due to the prevention or healing of microcracks or holes. Bulychev et a1.14 observed that cracks and voids in initially prestrained copper were healed in the necked region of a tensile specimen upon further straining while under a superposed pressure. Also, pugh5 observed that large cavities were suppressed in copper fractured in tension while under pressure. A second proposal has been forwarded by Beresnev et at al.6 This proposal is based upon the hypothesis that a material fails in a brittle manner because the normal tensile stress reaches a critical value before the shear stress is of sufficient magnitude to cause plastic flow. Since a superposed hydrostatic pressure will increase the ratio of shear to normal tensile stress, a sufficiently high hydrostatic pressure should favor plastic flow while retarding brittle fracture. Galli15 reported that a superposed pressure shifts the ductile-brittle transition temperature of molybdenum. This was explained based upon the reduction of the normal tensile stress by the superposed pressure. Pugh5 explained the occurrence of the observed pressure induced brittle-to-ductile transition in zinc in the same manner. Davidson et al.12 proposed an explanation for the enhancement of ductility by pressure based upon the effects of pressure upon the stress-state-sensitive stages of various fracture propagation mechanisms. Basically, they proposed that pressure will retard cleavage and intergranular fracture by counteracting the required normal tensile stress or will suppress void growth. They observed suppression of intergranular fracture and void growth in magnesium by pressure. Davidson and .Ansell16 reported ductility as a function of pressure for a series of annealed and spheroidized Fe-C alloys. Fig. 2, from this prior work, demonstrates that the effect of pressure upon ductility is structure sensitive in terms of the amount, shape and distribution of the brittle cementite phase. As shown in Fig. 2, in the absence of cementite or when the cementite is in isolated particle form (spheroidized), the ductility-pressure relationship is linear and the slope decreases with increasing carbon content. In the annealed carbon-bearing alloys wherein the cementite is in the form of closely spaced platelets (pearlite) or in the form of a continuous network along prior aus-tenite boundaries (1.1 pct C material), ductility as a function of pressure is nonlinear (polynomial relationship) in which the slope increases with increasing pressure. At the highest pressures studied (22.8 kbars), the slope of the curves for these materials tends to approach those for the spheroidized material of the same carbon content. In this current investigation the change in fracture mechanisms as a function of pressure for the materials shown in Fig. 2 has been examined. The possible connection between the observed effects of pressure upon the fracture mechanisms and the effect of pressure upon ductility is discussed.

Jan 1, 1970

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By Harry A. Wahl

Precent fracture design procedures are bared on the total fracture area created. A method to distinguish beI,,.ecn total area and [he propped or effective fracture area has not been available. This paper presents a solution to this problem, applicable to horizontal fractures. The difierences between effective fracture area and torn] area are demonstrared in example calculations. This work is hayed on experimentally determined transport efficiencier of solids in sand-liquid slurries. Newtonian and non-Ne~vtoninn systems are considered. INTRODUCTION Fifteen years after commercial introduction, hydraulic fracturing remains the most successful stimulation technique in the oil field. This success is primarily due to ability of induced fractures to penetrate and alter permeabilities deep within formations. Many fields producing today could not have been developed without the hydraulic fracturing process. Because of wide usage, fracture-treatment design has received a great deal of engineering and research effort. This work, resulting in improved equipment and materials, has increased the benefits from fracture treatments as well as the applicability of the process. A major contribution was the development of fluid-loss additives. Necessarily, the number of parameters to be considered in treatment design has steadily increased, resulting in more complicated design techniques. Almost all present design procedures are based on the precepts set forth by Howard and Fast. Relating the fluid volume lost into the formation, the volume required in extending the fracture, and the total slurry volume injected, they developed an expression for the total fracture area created in terms of pertinent treatment parameters. Fluid loss during treatment was expressed as a function of time for three flow mechanisms. Although modifications of fluid loss equations have been made, the total fracture area concept has remained unaltered. A vast amount of field data indicate that induced fractures must be propped and held open to be effective. A notable exception is the Mesa Verde formation in the San Juan basin. However, analysis of these treatments shows that improved well productivities are obtained when propping agents are incorporated in the treating fluid. Although propped fracture area has been recognized as an important design parameter, a method to distinguish between total area and effective fracture area has not been available. The necessary information on slurry-sand transport in fractures has been lacking. Interest in the propped region of induced fractures is not restricted to areal extent alone. The distribution of sand within fractures is important from the standpoint of fracture flow capacities. Flow capacity affects the increase in well productivity after stimulation. The work of Huitt and Darin4 hows that partial monolayers of sand have large flow capacities compared to thick* dense sand packs. It has been postulated that gelled fluids have the ability to transport sand within the fractures at the deired low concentrations. An early contribution in the area of sand placement in fractures was made by Kern et al.' They studied sand movement in a transparent vertical fracture model. It was observed that the sand tended to settle out in the bottom of the model before moving very far. When the fluid velocity exceeded a certain critical value, all of the sand injected began moving through the crack even though it settled to the bottom. This critical velocity was determined under several flow conditions. Some work on sand movement in horizontal fractures has been reported in Russian publications. Sand movement was studied by Izyumova and Shan'gin' using a transparent "pie-shaped" flow model to simulate a horizontal radial flow system. However, the data were limited, especially in a quantitative sense. Dorozhkin, Zheltov and Zheltow studied the behavior of sand-liquid slurries in a horizontal linear flow model. The quantitative data were restricted primarily to the thickness of sand deposits formed at the bottom of the fracture. An earlier paper provided basic data on the flow of sand in horizontal fractures. This study was designed to yield specific quantitative information on rate of advance of sand particles and pressure behavior under various flow conditions. A comprehensive photographic study was undertaken in a 10-ft windowed flow cell to provide the necessary qualitative and quantitative data. Since the number of potential variables far exceeded the capacity of the initial study, emphasis was placed on the effects of sand concentration, oil viscosity and oil flow rate. A detailed description of these experiments and the results are described in Ref. 9. However. the implications of this work on the fracture design calculations were not discussed. An analysis of these data as well as new data is provided in the following sections. EXPERIMENTAL RESULTS The primary objective of the experimental investigation was to provide information on the rate of advance of the solids in sand-liquid sturries. A 10%-ft long transparent

Jan 1, 1966

By W. R. Hansen, F. W. Boulger

Twenty-nine laboratory steels were studied to determine the effects of composition and ferrite grain size on drop-weight and Charpy V-notch transition temperatures. The experimental steels covered the following ranges in composition.. 0.10 to 0.32 pct C, 0.30 to 1.31 pct Mn, 0.02 to 0.43 pct Si, md nil to 0.136 pct acid-soluble Al. Although most of the data were obtained on hot-rolled samples, some plates were heat-treated in order to cover a wider range in ferrite grain size. The experimental data were used for a multiple-correlation analysis conducted with the aid of an electronic computer. The study showed that carbon raises and that manganese, silicon, aluminum, and finer ferrite grains lower both drop-weight and Charpy transition temperatures. Quantitatively, variations in composition and grain size have a more marked effect on V15 Charpy transition temperatures than on the drop-weight transition temperature. Useful correlations were found between transition temperatures in drop-weight tests and those defined by seven different criteria for Charpy tests. Evidence was accumulated that the conditions ordinarily used for drop-weight tests are more severe for 1-1/4-in. -thick plate than for 5/8- to 1-in. -thickplate. PROJECT SR-151, to study quantitatively the effects of metallurgical variables on performance in the drop-weight test, was established by the Ship Structure Committee late in 1958 on recommendation of the National Academy of Sciences, National Research Council. This project was initiated as a result of the increasing use of the drop-weight (nil-ductility) test in predicting the ductile-to-brittle behavior of steel. Qualitative data indicated the drop-weight was not as sensitive to metallurgical variables as the Charpy V-notch test. Furthermore, the available information indicated that the drop-weight test did not show the superiority of killed steels over semikilled steels reflected by Charpy tests. This difference in sensitivity to brittle fracture is considered important because the drop-weight transition temperature has been reported1 to correlate better with service-temperature failures than the V-notch test does at a constant energy level. Therefore, this project was concerned with establishing quantitatively the effects of metallurgical variables in the drop-weight test. For comparison, Charpy V-notch data were obtained for the steels investigated. This paper summarizes the results of the investigation. Most of the steels used for the study were made and processed in the laboratory. However, some tests were also made on commercial killed steels available from Project SR-139 (SSC-141). During the course of the investigation, data were obtained on the effects of carbon, silicon, manganese, and aluminum on transition temperatures of drop-weight and Charpy specimens. In addition, the effects of heat treatment which changed the ferrite grain size and the transition temperatures were also investigated. Finally a few exploratory studies were made on commercial killed steels to evaluate the effects of plate thickness, grain size, and heat treatment on the performance of drop-weight specimens. EXPERIMENTAL PROCEDURES Preparation of Materials. A total of twenty-nine 500-lb induction-furnace heats were made and processed in the laboratory for the investigation. Carbon, manganese, silicon, and aluminum contents were systematically varied. Melting and rolling techniques proven satisfactory in a previous project2 were used as a guide for the current investigation. Composition. The composition of the twenty-nine laboratory heats made for this project are given in Table I. The steels are divided into three groups. The first group consists of ten aluminum-killed steels similar in composition to Class C ship-plate steel. The second group consists of ten semikilled or Class B type steels. In both of these groups the carbon and manganese contents were intentionally varied over a wide range. This wide range in composition was helpful in obtaining quantitative data from a limited number of steels. The primary purposes of these two groups of steels was to determine the effects of carbon, manganese, and deoxidation practice. In addition, one steel in each group (Steels 2-2 and 9-2) were made about 1 year after the start of the program in order to check consistency of melting practice. The third group of nine steels listed in Table I was intended for studies on the effects of silicon and aluminum. In eight of these steels carbon and manganese were held relatively constant at levels of about 0.2 and 0.8 pct, respectively, while silicon and

Jan 1, 1963

By Alfred Weiss

Approximately 850 delegates from 24 countries met in Tokyo, Japan, May 24-27, for the second MMIJ-AIME Joint Meeting in 55 years, to exchange technical knowledge and experience in the fields of exploration, mining, metallurgy and petroleum engineering. The first such meeting was held in 1917 in Kyoto, Japan. Although the Mining and Metallurgical Institute of Japan was the sponsor, the entire meeting (machinery exposition, technical program, and tours) was a joint effort of the two institutes.

Jan 7, 1972

By D. J. Christie, W. C. Hellyer

Three autogenous grinding flowsheets were considered as follows: 1) Primary autogenous grinding of a -8-in, primary crusher discharge to produce a product suitable for second stage pebble milling, or a flotation feed product in a single stage of grinding. 2) Intermediate autogenous grinding in which +4-in. rock media is screened from the primary crusher discharge and employed as grinding media to grind a tertiary crusher product to flotation feed size in a single stage.

Jan 8, 1972

By Johnston, T. L.

BISMUTH is found as native metal associated with tin, copper, cobalt, silver, gold, or other metals and in a variety of ores. The more important ones are: bismuthinite (bismuth glance), Bi2S3; bismite (bismuth ochre), Bi2O3.3H2O; and bismutite (bismuth carbonate), Bi2O3CO3?H2O. Of lesser importance are the arsenate, telluride, and vanadate. The sulfide is the most common; the others are often oxidation products from this mineral. Bismuth minerals have been found in various places in the United States, principally in Colorado and Utah, but no ores are mined solely for bismuth. In the Granite mining district of Beaver County, Utah, a stratum of limestone about 6 ft. thick has been almost completely replaced by contact minerals in which bismuthinite associated with pyrite and molybdenite was found intergrown with silicate minerals. In the early days a few small lots of ore assaying 7 to 10 per cent bismuth were shipped from this district. Native bismuth has been found in the Clifton and Tintic districts of Utah. Bismuth is produced as a byproduct in the refining of lead, copper, gold and silver ores, it being recovered from the anode mud from the Betts process. Deposits of bismuth minerals exist in Argentina, Aus¬tralia, China, Japan, Germany, Spain, Peru, Bolivia, and Canada, but Bolivia is the principal, producer and could easily supply all of the present world's demand.

Jan 1, 1933

By Herbert Hoover

DURING the year, the' Institute has made the most remarkable growth in its history. Our actual increase in membership was 1816 and therefore was 80 per cent. larger than any previous year. Even without expectation of any abnormal growth, we should pass in the year 1921 the 10;000 mark. The causes of this increased growth are not far to seek.. They lie in the widening vision of the Institute's work, not only in its relation to' the profession but as an avenue of service to the nation as a whole. The Institute is today in the first rank of influence among public institutions in the country. During this year we have, for the first time in many years, had a ?deficit of some $3000 in our finances. The sum is not important, but it- does indicate the tendency of the times, and that is the high cost of living:' The increase in our expenses lay, to the largest degree, on the publishing side of the Institute's work. If we compare the year 1918, as a fairly repre¬sentative year, with that of 1920, we find that the costs of issuing the' Institute's publications, after deducting the income received from these publications, shows a .net increase of about $33,000. for the year. This has been to some degree due to the enlarged membership but to a large degree due to the cost of the paper and printing.

Jan 1, 1921

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand these has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of —200 mesh material in the final product markedly increases costs of de-watering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins. Wasting of coal in the -200 mesh slimes may account for a loss in washer yield equivalent to 2.0 to 2.5 pct of the raw coal input. With rising mining costs the value of such a loss is constantly increasing and a need for a better solution to the fines problem becomes more pressing every day. From an operating viewpoint, also, continuous removal of extreme fines from the washing plant circuit permits good water clarification practice, improving significantly the overall cleaning efficiency. The obvious desirability of recovering a commercially acceptable coal from washery slimes prompted U. S. Steel Corp. to investigate the merits of the Convertol process developed in Germany." Although this process has been used commercially in Europe for some time, little if any consideration has been given to its possible adoption in the U. S. until very recently. Fundamentals of the Convertol Process: In the Convertol process, droplets of dispersed oil are brought into intimate contact with the solids suspended in the coal slurry to be treated. This contact causes oil to displace the water on the surface of the coal by preferential wetting, or phase inversion, after which the coal particles are allowed to agglomerate in a manner permitting their re- moval from the slurry by centrifugal filtration. The clay and other particles of mineral matter suspended in the slurry do not have the affinity for oil the coal particles have. Consequently the oil treatment is preferential to coal to the extent that more than 95 pct of the oil used reports with the clean coal recovered. Figs. 1 through 3 will clarify the steps involved in the process. Fig. 1 shows the suspended material in the slurry to be treated, which is a thickened product containing 40 to 45 pct solids. Oil is now injected into the slurry under vigorous agitation to produce good oil to coal contact conditions, which result in preferential oiling of the coal particles. These coal particles are then permitted to agglomerate by gentle stirring in a conditioner to form flocs, as shown in Fig. 2. At this point in the process the agglomerated oiled coal can be washed and partially dewatered on a vibrating screen, as shown in Fig. 3. Finally, the washed flocculate can be further dewatered in a high-speed screen basket centrifuge or in a solid bowl centrifuge. Commercial Application of the Convertol Process in Germany: The original Convertol process was developed by Bergwerksverband zur Verwertung von Schutzrechten der Kohlentechnik, G.m.b.H., a German research organization controlled by the Coal Operators Assn. of the Ruhr Valley. The process as reduced to commercial practice in Germany' is shown in Fig. 4. In this process a thickened slurry (40 to 45 pct solids) mixed with a predetermined percentage of oil is fed from a surge tank to the phase inversion mill. After the phase inversion step, the slurry is usually discharged directly to a highspeed screen centrifuge. From 3 to 10 pct oil is used, depending on type of oil, size consist of coal to be recovered, and operating temperature. The top size of fine coal cleaned in Germany by the Convertol process is limited by the size of the openings in the centrifuge screen basket. Any mineral matter coarser than the basket opening, which is generally 60 to 80 mesh, must remain with the oiled coal. If the coal fines have been effectively cleaned down to about 80 mesh, the cleaning performance of the process is practically unaffected by the presence of coarse coal particles. However, since recovery of coal much coarser than 80 mesh is mow economical by conventional methods, it normally becomes more costly to allow substantial percentages of this coarse coal in Convertol process feed. Where the general plant layout does not permit effective cleaning of coal sizes down to 80 mesh or lower. there is some justification for a coarser Con-

Jan 1, 1959

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.' This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6' At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963

By D. R. Parrish, T. M. Geffen, R. A. Morse, G. W. Haynes

Flow tests on small core plugs have indicated that a large amount of gas is trapped and not recovered by water flooding a gas sand. Instead of I to 15 per cent pore space, as is usually assumed, the residual gas saturation is 15 to 50 per cent pore space, and is thus of the same magnitude as residual oil after water flooding oil sands. A thorough investigation was made to ascertain that large amounts of residual gas actually remain in reservoirs after a water flood and that this condition is not merely a laboratory phenomenon. In field experiments, the amount of gas left in a watered-out gas sand was measured by use of a pressure core barrel and the residual gas saturation of two watered-out gas sands was determined by electric log evaluation. In the laboratory, an investigation was made of factors that could possibly cause the value of residual gas saturation as measured on small core plugs to differ from that in the reservoir, and the effect of these factors on the amount of residual gas saturation was studied. The factors studied include flooding rate, static pressure, temperature, sample size and saturation conditions before flooding All evidence established that a relatively high gas saturation is trapped in water flooded gas sands and that this residual gas saturation can be measured in the laboratory by tests on small core plugs. INTRODUCTION There. has been general agreement among engineers that very high recovery of gas could be obtained from natural reservoirs By water displacement. Gas recoveries of 80 to 95 per cent of the original gas in place have become the normal expectation in water drive fields. The assumption of high recovery has been based on: 1. low density and viscosity of gas compared with water; 2. the erroneous assumption that the flow relationship in a gas-liquid system where gas is the displaced phase will be the same as when it is the displacing phase. It has long been recognized that gas can flow at very low gas saturations (in the range of 1 to 15 per cent pore space) in systems where liquid is being displaced by gas. By assuming the reversibility of this process, the conclusion was reached that the residual gas saturation following water flooding of a gas reservoir would be the qame (1 to 15 per cent) as that at which gas first flowed continuously as a displacing phase. Recent laboratory relative permeability Studies have demonstrated that the flow characteristics are very different in gas-liquid systems, depending on whether gas is displacing or being displaced by, a liquid. Also, it has been shown that there is no difference between the flow characteristics of oil and water or gas and water in water wet porous rocks. The residual gas saturation that can be expected following water flooding of a gas reservoir then would be in the same range as the residual oil saturation normally expected after water flooding an oil reservoir! i.e., in the range of 15 to 50 per cent pore space, depending on the rock characteristics. Obviously, such a difference in residual gas saturation means very important differences in recoverable gas reserves from water drive reservoirs. For example, if the original gas saturation in a field were 70 per cent, and the residual gas following flooding were 35 per cent, only half of the gas in place could be recovered by complete water drive, compared to the previously expected 80 to 95 per cent. This is a situation in which complete pressure maintenance could result in very greatly reduced recovery, since straight pressure depletion recoveries from gas reservoirs can approach 80 to 90 per cent. Such a change in thinking must be based on more complete information than a series of small core tests. Hence the work reported herein was undertaken with the objective of determining whether or not residual gas saturations indicated from small core relative permeability tests at atmospheric pressure and room temperature are representative of the residual gas saturations which could be expected after water flood of natural reservoirs. A study was made both through laboratory and fields tests to determine any differences in residual saturation which might be occasioned by differences in pressure, temperature, rate of flooding, and original saturation conditions. Four separate types of laboratory experiments and two field mesurements were made in this investigation. The apparatus and testing methods of each will he discussed individually. LABORATORY EXPERIMENTS, APPARATUS AND PROCEDURE Relative Permeability Tests Steady state flow experiments Here conducted using the Penn State type apparatus. The equipment used has beer (described in a previous publication? "Irreducible" water satu-ration was established in the core' by imposing ,a capillary pressure of 45 psi before simultaneous flow of air and water

Jan 1, 1952

By O. A. E. Jackson

Pebble milling has been practiced in the reduction works of South Africa gold mines for well over 50 years. Originally flint pebbles were imported from Denmark to grind stamp-mill amalgamation-process tailing, which contained a good deal of extractable gold, but local operators soon found that large pieces of ore could be used for the same purpose. The ore is a hard, tough conglomerate in which quartz pebbles are cemented together by a matrix of redeposited silica interspersed with pyrite crystals. The gold, rarely visible, occurs as fine particles mostly segregated at the interface of the pebble and matrix, although a small fraction occurs within the pyrite crystals. There is seldom any gold in the pebbles themselves. Following the usual South African practice in pebble milling, Union Corp. grinds the ore wet in two or three milling stages incorporating classification. The sized broken ore used as grinding media is separated from the main ore stream in the crushing section that prepares the ore for milling. Where the ore channel, or reef, is narrow there is a shortage of large pebbles. In this case primary grinding may be done in ball mills or, more recently, in rod mills, which cost less per ton to operate. The trend, however, is to prepare finer feed for the milling section. This makes it possible to use smaller primary pebbles and eliminates the need for steel. REDUCTION WORKS OF UNION CORP. LTD. Union Corp. Ltd. exercises financial and technical control over a group of seven gold mines in the Transvaal and Orange Free State. In the Transvaal, with one exception. the mines lie 20 to 40 miles east of Johannesburg, in flat or gently rolling countryside. Winkelhaak, the first of several new mines that will be developed by Union Corp., is located in similar terrain in an entirely new gold mining district about 80 miles east of Johannesburg. Table I gives details of milling units for six of the Union Corp. mines, together with the tonnage milled in 1957. Winkelhaak Mines Ltd. is not included, as it did not begin milling until 1958. This reduction plant has no crushing section; ore is ground directly from the mine (autogenously) in 12x16-ft mills. Because these operations are still in development, they are not described in this article. It will be noted that certain reduction works have mills of more than one size in the same milling stage. This came about when plant extensions in- corporated larger units. In the case of Geduld Propty. Mines Ltd., which began milling operations 50 years ago, the primary stage is stamp milling. The reduction works follow a uniform pattern and are usually joined to the main ore shaft. Ore from other shafts is brought by standard-gage railway and dumped into a common transfer bin. The trend is to increase surface storage capacity to enable the crushing and milling sections to operate at a steady rate, independent of fluctuating ore deliveries from mine. Milling and cyanide extraction divisions of new mines are always designed to allow for extensions as mine production increases. The conveying, washing, and screening system of the crushing section is usually laid out in final form, with additional space for more crushing equipment. The crushing sections operate on one shift during early years of mine production; a second shift is introduced when the mining rate warrants it. Ample surge capacity is provided. Crushing and milling is done only on weekdays, as the law does not allow these operations to take place on Sunday in any plants constructed since 1911. The cyanide extraction sections, however, operate continuously seven days a week, drawing on mill pulp gradually built up in the thickeners during the week. Construction and equipment of milling plants follow standard practice. Dilution water is drawn from a large, high-level tank to obtain constant pressure, but gland service water for the pulp pumps is reticulated from high-pressure, two-stage pumps. The mills are equipped with the most up-to-date machinery and are designed to save labor. They compare favorably with milling plants in countries where native labor does not exist, and automatic controls are being installed wherever feasible. Hydrocyclone classifiers have replaced mechanical classifiers in modern milling plants, chiefly because of the saving in capital outlay, maintenance, and building space. The hydroclones are fed from steady head boxes rather than directly from pumps, and dilution water is introduced into these boxes. Tests have shown that in steadiness of operation and separating efficiency cyclones are comparable to mechanical classifiers. but protective stationarv screens are needed to keep the spigots clear. Rubber-lined pumps are used for pulp of about 3 mesh or finer and metal-lined pumps for coarser material. None of the Union Corp. milling plants practices gravity concentration of coarse gold by amalgamation or the use of corduroy blankets. Studies have proved that no economic case can be made for these methods, which complicate the milling process and demand extra precautions against theft.

Jan 1, 1960

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper' the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called ('deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,' it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2'3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,' indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By Alfred Boyles

"Heredity"1 in cast iron has been a subject of much discussion. Numerous experimenters have found that the properties of gray iron may vary greatly without corresponding variations in composition or thermal treatment. The main structural difference in such cases is in the size and distribution of the graphite flakes and the explanations given usually attribute this difference to some chemical element not shown by ordinary analysis or to some physical factor, such as inclusions in the melt. It cannot be said that any of these theories is completely satisfactory. Much remains to be learned about cast iron and for this reason a study of the material was undertaken as a part of the program of fundamental research at Battelle Memorial Institute. A review of the literature indicated that very little systematic work had been done on the mechanism of freezing in cast iron. The experiments described below are largely concerned with that problem. Normal and "Dendritic" Cast Iron As examples of variation in type of structure, photomicrographs of two test bars of cast iron are shown (Figs. 1 and 2) and the composition and properties are given in Table 1. Both are common, unalloyed gray iron. Test bar No. 13 has normal graphite flakes while No. 49 has very fine, lacy graphite arranged in a dendritic pattern, the matrix in both being pearlite. These two types of cast iron are well known to foundry-men and need no detailed description.

Jan 1, 1937

Discussion of "The Ordering Transformation in Titanium-Aluminum Alloys Containing up to 25 at. pct Aluminum" by F. A. Crossley, Trans, TMS-AIME, 1968, vol. 242, pp. 726-30. Dr. Blackburn, in his response, pointed out that the c/a ratio of the Ti-26 at. pct A1 alloy quenched from 900°C is 1.6006 and not 1.5965 as plotted in Fig. 19. An error in transcription was made in preparing Table V of Ref. 1 (F. A. Crossley, Trans. TMS-AIME, 1966, vol. 236, p. 1174). The corrected Fig. 19 strengthens rather than weakens the argument that a martensitic transformation occurs in alloys containing from 15 to 18 at. pct Al. A Study of the Factors Which Influence the Rate Minimum Phenomenon During Magnetite Reduction, by P. K. Strangway and H. U. Ross, Trans. TMS-AIME, 1968, vol. 242, pp. 1981-88. Page 1883 Reverse Figs. 5 and 6. Sigma—Its Occurrence, Effect, and Control in Nickel-Base Superalloys, by J. R. Mihalisin, C. G. Bieber, and R. T. Grant, Trans. TMS-AIME, 1968, vol. 242, pp. 2399-2414. Pages 2403, 2407, and 2414 Arrows should appear on Figs. 4 and 9; a sigma is missing from Table IV; line 2, page 2414, change "case" to "cast". These are published correctly in the bound volume. Index, December Issue There were a few omissions in the Author Index. These have been corrected and published properly in the bound volume.

Jan 1, 1970