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By G. T. Engel, W. G. Gruzensky

Jan 1, 1960

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By J. Moore, D. Gault, R. V. Lugn

Impact of small projectiles with velocities between 0.9 and 7.3 km per sec on basalt produce craters chiefly by the ejection of fragments. Weight-size distributions of the ejecta are linear for part of the size range of the fragments. Cumulative weight-size distributions of the ejecta from different craters vary because of erratic formation of large fragments and a large percentage of ejecta below 0.1 mm. In the range of velocities studied, the crater depth is approximately proportional to the 0.75 power of velocity of the projectile. This relationship may represent a transition regime between the fluid impact regime and the undeformed projectile impact regime. The volumes per unit of projectile energy of the craters produced are comparable to those reported for lower speed projectile impact and drill bits. An experimental investigation of projectile impact on rock is being conducted jointly by the Ames Research Center of the National Aeronautics and Space Administration and the U.S. Geological Survey. Projectiles are launched with light-gas guns at the Ballistics Range of the Ames Research Center. The craters and ejecta produced in these experiments are being studied by the U.S. Geological Survey. Steel, aluminum and polyethylene projectiles weighing from 0.25 to 0.015 g were accelerated to velocities of 0.88 km per sec (2,900 fps) to 7.3 km per sec (24,000 fps) with a light-gas gun, using hydrogen as the propellant medium. Projectiles impacted the targets normal to plane rock surfaces in an atmosphere of air with a nominal pressure of 25 to 50 mm of mercury. The metal projectiles were mounted in supporting four-piece nylon sabots, which guided the projectiles down the launching tube. After launch, aerodynamic drag acted to separate the sabots from the projectiles. Impact velocities were determined with time measurements and spark photographs of the projectiles in flight. Ejecta were collected in lucite and aluminum containers placed around the target block. A small hole in the containers permitted projectile entry. Impact of projectiles of the size employed produced craters in the rock targets chiefly by ejection of fragments. The craters are small, roughly conical depressions with crushed and intensely fractured rock at the bottoms of the depressions. The ejecta are composed of pieces of the projectile and rock fragments ranging in size from a few tenths of a micron or less to several centimeters in maximum dimension. In this paper, the structural features of the craters, the weight-size distributions of the recovered ejecta, and crater depth and crater volume relationships are described. DESCRIPTION OF CRATERS Typical craters (Fig. 1) produced by experimental projectile impact in basalt are shallow, wide base

Jan 1, 1963

By Fred H. Perfect

The thermite process, now approximately 80 years old, has heretofore been practiced in ceramic vessels. This paper outlines the successful production of several million pounds of alloy produced in zuater-cooled copper vessels. THE high temperatures necessary to produce fluid high-alumina slags have probably discouraged earlier workers from attempting to utilize water-cooled vessels. The following is a report of the successful application of this method, together with a report of the physical and chemical problems which had to be solved to make the process practical. About 1955, when Reading Alloys was more concerned with the production of ferrotungsten than with most other types of alloys, it was found to be exceedingly difficult to predict the reaction rate that one would experience from one tungsten ore to another . This difficulty was increased for two reasons: the physical state of the ore as received was seldom uniform, and the size of the mass to be reduced is a very important factor in developing the proper mix for the final reaction rate and temperature. For example, the reduction of ferric oxide with aluminum would theoretically produce temperatures of about 2600°C, and, in spite of the losses due to radiation, the energy is quite sufficient to produce a very fluid slag and iron effecting a very clean separation. On the other hand, the reduction of ferrous oxide with aluminum, while it is not as energetic as the first reaction, nevertheless should give temperatures above 2000"C, which should cause separation of alumina and iron, but, in practice, this is not the case and good fluid slag is not obtained. The heat of reaction, calculated from the thermo-dynamic heats of formation of the constituents of the reaction, offers a convenient guide to the feasibility of a thermite reaction. Thus, the values listed in Table I can be used as an approximate guide for estimating the results which may be expected in the reduction of various oxides and combinations of oxides using aluminum as the reducing agent. As a generalization, those reactions releasing approximately 600 cal per g of total mass represent the lower limit at which to expect separation of slag and metal. On the other hand, those reactions which release 1100 to 1200 cal per g are too violent to be used successfully without the addition of considerable inert material, such as lime, fluorspar, and so forth. Reaction rate is also a very important factor. This, of course, is governed very largely by the sizing and intermingling of the oxidant and reductant and by the starting temperature of the reactants. This is why those figures shown in Table I can only be a general guide. Further, it must be understood, that by adding powerful oxidizing agents, such as nitrates, chlorates or metallic oxides, such as molybdenum trioxide or chromium trioxide, certain problems respecting low temperatures are not necessarily solved. This is true in the addition of oxidants, such as sodium chlorate. By adding too high a concentration of sodium chlorate as a booster for a particular reduction, explosions are generated. Generally, they are of an intermittent type so as to give a Roman Candle effect to the reduction itself; with each surge resulting from a minor explosion more and more material is thrown

Jan 1, 1968

By P. T. Allsman

INTRODUCTION The honor of being the recipient of the Mining Society's Daniel C. Jackling Award for 1966 imposes on me the responsibility to search for the subject that I would be best qualified to discuss. It seems that my experience in the mineral industry — nearly 15 years in private and 30 years in public employment — should uniquely qualify me to comment upon the relationships between the mining industry, mineral engineering as a profession, and government, and the changing economic, technologic, political and social changes that dictate their relationships. Such conditions, the increasing knowledge of the world mineral resource base, the greater demands of an expanding population with a rising standard of living, shall be evaluated with respect to our profession — mineral engineering. In all of these forty or so years, I have been in close touch with many phases of the mineral and energy resource industries, especially those of the United States. Particularly during the past 10 years, I have had a ringside seat at the "goings on" in Washington. During all of this period I have observed and analyzed many of the problems of the industry and its relations with the government. During the past few years, I have had increased opportunity for doing research and have found a need to learn something about the mathematical techniques that are undergoing such a revival since electronic computers were developed. One of these techniques is multivariate analysis, which is a system for correlating a large number of complex variables. By applying this technique to the seemingly chaotic present-day situation, there emerges a course of steady improvement in the minerals resource industries that wars, depressions, and political strife have failed to obstruct for long. In short, I advocate a need for new concepts in mineral engineering to cope with the changes, pos- sibly adding many more specialized areas on one end of the spectrum, and broad engineer-generalist approaches at the other. The meeting place shall be where the intricate mineral resource problems at the frontier of knowledge merge into the socio-techno-logical problems of the world. HISTORICAL INVOLVEMENT OF GOVERNMENT IN MINERAL RESOURCE PROBLEMS Involvement of government in mineral resource problems undoubtedly is as old as government itself. But passage of the Mining Act of 1866, superseded by the Act of 1872, was the first major entry of our Federal Government into the problems of mining. Passage of the law was necessary to resolve many conflicting claims and disputes in mining. The General Mining Law of 1872 and the Mineral Leasing Laws of 1920 apply to millions of acres of public lands and to certain privately owned land on which the mineral rights have been reserved to the Federal Government. The extensive involvement of government in the mineral industry business today often comes as a shock to the mineral engineer who has begun to climb the ladder to the top in his company. He is often poorly prepared to cope with the situation and becomes frustrated and even hostile. Better knowledge of the role of government perhaps would ease his situation. In our political system, private industry is responsible for producing minerals. To make certain that the production is adequate for a peace-time economy, and to guarantee the Nation's security in an emergency, the Federal Government finds it expedient to develop policy and engage in regulatory, educational, and research activities. A few examples will illustrate the varied role of government in relation to mineral problems. In varying degrees many agencies of the Executive Branch of Government have responsibilities that influence the functioning of the mineral and energy industries. In addition, of course, Congress, the Judiciary, and State and local governments exercise great influence. The Department of the Interior is primarily responsible for activities to promote the development and conservation of mineral and fuel resources, and the

Jan 1, 1967

By S. H. Ward, R. A. Barker

THE Juniper Prospect is in Carleton County, N. B., at approximately 46" 31' north latitude, 67" 20' west longitude. During the summer of 1955 an area in west-central New Brunswick was selected for aerial electromagnetic prospecting with American Metal Co.'s helicopter-mounted equipment. Generalized, small-scale government geologic maps had suggested that this area was located along the western border of the northeast-trending granitic backbone of northwestern New Brunswick and might be underlain by the Ordovician-Silurian sediments and volcanics that are the host rocks for the recently discovered sul-fide deposits of the Bathurst-Newcastle district. The helicopter electromagnetic equipment located an anomalous conductive area, coincident with a small aeromagnetic closure, about five miles west of the town of Juniper. Subsequently 30 mining claims (total area about 6600 x 8000 ft) were staked and company personnel conducted geological, geophysical, and geochemical investigations on the property. The claims and immediately contiguous areas were mapped geologically, and an area of about 2000 x 4000 ft was soil-sampled and also surveyed by ground electromagnetic and gravity methods. Finally six diamond drillholes, totaling 3500 ft in length, were drilled to test the anomalous conditions discovered by the several exploration techniques used. The discovery of base metal sulfides during drilling was a technical success for the exploration methods, but the quantity of sulfides was too small to be profitably exploited.

Jan 1, 1959

By John F. Wiggert

DURING the early years of Homestake operations, shaft signaling from the cage tenders to the hoisting engineers was done by mechanical means. Small steel cables or jointed steel rods were suspended in the shaft compartments and counterbalanced with weights or springs. These cables or rod strings were connected to the mechanically operated gongs at the engineers' stations by means of bell cranks and steel wires. The system was simple and economical and served the purpose well until the mine reached a depth of 1000 ft., then the system became slow and cumbersome and required a considerable amount of muscular effort to operate it with much speed, because of the inertia of the heavy moving parts. The mechanical signaling was superseded by a simple electrical system consisting of a single pair of wires in steel conduit for each shaft compartment. In the shaft at each station a pull switch was connected to the wires. The switches were operated by means of bell cords, which extended from station to station. This electrical system was a great improvement over the mechanical one, but it had one serious drawback, which also applied to the older system; namely, the engineer did not know where a signal originated. Later on this signaling was improved to overcome this drawback, and to give the engineer a positive indication of a signal's origin. In this system a separate return wire from each pull switch is carried to an annunciator at the engineer's station, where it indicates the signal's origin. While the annunciator system used by Homestake is very safe and reliable, it has the inherent drawback of all wire-connected systems in that it is impossible to send a signal from a moving cage. A number of years ago Homestake became interested in the possibility of using some sort of radio transmission for shaft signaling. The company did much experimental work with purely radio signal transmission, but no practical way was discovered to use radio transmission in a mine shaft for signaling to or from a cage. Therefore, all efforts were directed to devising a practical way of using the hoisting rope as part of the circuit. It was realized that the return circuit from the rope would need to be through electrostatic coupling between the cage and the earth or ground sides of the shaft, because the guides would not always be wet enough to make possible good electrical contact between the cage and earth, therefore relatively high-frequency alternating current was chosen as the medium of transmission. Soon a practical system was developed for transmitting an electric current from a moving cage over an electric circuit of which the hoisting rope was a part. A high-frequency electric current is used as a carrier to transmit the signals or mes-

Jan 1, 1941

The program of 'the Chicago meeting, which is to be held Sept. 22-26, is as follows: Monday. Morning-Registration. Afternoon-Technical Session. Evening Smoker. Tuesday. Morning and Afternoon-Excursion by boat to Gary and trip, through United States Steel Co's. plant. Evening-Technical Session. Wednesday. Morning- Technical Session. Afternoon-Technical Session. Evening-Banquet, Congress Hotel. Thursday. Morning and Afternoon-Special train to La Salle and De Pue, Ill., Inspection of Zinc Smelters, Cement Works, and Coal Mines. Trip to Starved Rock and points of historical interest. Evening-Return by train to Chicago. Friday. Morning-Optional trips. 1. East Chicago Metallurgical Plants and Oil Refineries at Whiting, Ind. 2. North Chicago and Milwaukee. 3. Local Chicago Plants. 4. Coal trip to Franklin and McCoupin Counties.

Jan 6, 1919

By R. J. Colony

DEPOSITS of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residua] limonite at the west end of the island near Mayaguez1-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7-9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugues, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By W. A. STERLING

IN the opencut iron mines of the Mesabi Range in Minnesota, the trend in mining is in the development of mining equipment and mining methods which will move surface overburden and ore-bearing materials with less labor and at a cheaper cost. This is a must for most of the independent operators. Their reserves of direct-shipping ore are extremely small and their operations are being conducted in small, or intermediate pits, with a high stripping ratio in the outer fringes, or shore lines of older pits. and in ore bodies passing from direct shipping to the washing and the intermediate, or retreat ore state. The trend is toward deeper stripping, longer and steeper hauls, and the necessity of moving a total of from three to five or six tons of overburden and ore material for each ton of shipping-grade ore produced. This naturally calls for greater production, with larger shovels, or draglines. cheaper drilling and blasting costs through the drilling of larger-diameter blastholes, and cheaper haulage through the use of trucks of larger capacity and more extensive use of belt-conveyor systems. This trend is notable both in stripping and mining.

Jan 1, 1948

By Donald J. Knight

HEAT Treatment at 1500' F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as 'A', Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point 'C', which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By C. C. Miller, A. R. Belyea, C. H. Herty, E. B. Burkart

The removal of sulfur from steel has been studied by many investigators, but the quantitative relationships between the factors involved have not been determined. This is undoubtedly due to the number of variables encountered in practice, an attempt to study any one reaction or relation being affected by other reactions the relative importance of which cannot be estimated. The factors that affect the extent of removal of sulfur in the basic open-hearth process are generally considered to be: 1. Basicity of the slag: (a) Iron oxides in the slag; (b) carbon in the metal or carbide in the slag; (c) temperature. These factors affect the reactions: FeS + CaO = CaS + FeO FeS + CaO + C = CaS + CO + Fe. 2. Amount of sulfur in the gas. 3. Amount of manganese in the metal. The factors which affect the rate of removal of sulfur include, in addition to these: 4. Fluidity of the slag: (a) Normal changes in fluidity with temperature; (b) changes in fluidity because of the addition of special reagents such as fluorspar. 5. Agitation of the bath. Within the past two years, two papers have been presented dealing with the influence of sulfur in the gas on slag and metal. Nead' has shown that if a gas high in sulfur be used for heating, the metal and slag will absorb sulfur. Whitely2 concluded from his experiments that if a

Jan 1, 1925

By D. R. Cook

This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. The project was based on the idea of W. S. Burbank, U. S. Geological Survey, that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Here, an area of andesitic rocks, four square miles in extent, has been argillized, pyritized, chloritized and silicified. Geological, geophysical and geochemical studies were followed by the diamond drilling of three holes totalling 6,220 feet. Further alteration ang geochemical studies were made on the cores from these holes. A brief review of the alteration and geologic mapping, colored aerial photograph interpretation, geochemical soil and rock sampling, magnetic, gravity and radio-metric surveys are presented together with some conclusions regarding this work. This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. Important contributions were made to the project by personnel of the Rocky Mountain District and the Geophysics Division. Individual acknowledgements to these people are made at the end of the paper. BASIS FOR THE PROJECT The project was based on the idea of W. S. Burbank (1947, p. 444) that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Paleozoic sedimentary rocks, including the favorable Leadville limestone, are exposed three miles south of the altered area, and reason exists to believe that they might underlie it within a reasonable depth. Alteration of pre-mineral volcanic rocks has been used successfully as a guide to concealed orebodies in the Main Tintic and East Tin tic mining districts, Utah (Bill-ingsley, 1933, p. 120-122; Lovering et al, 1949; Howd, 1957, p. 124-134; Cook, 1957, p. 73) and could be a useful guide here. GENERAL GEOLOGY AND STRUCTURE The Northern and Southern Bonanza mining districts are northwest of the San Luis Valley in southern Colorado, just within the northeastern edge of the San Juan volcanic province. The districts are1ocated on the southern extension of the Sawatch uplift, a prorninent northwest-trending structural high. The highly productive mining camp. of Leadville, Gilman and Aspen are on the northeastern and northwestern flanks of this uplift where Paleozoic limestones have

Jan 1, 1961

COUNCIL OF ECONOMICS OF AIME Formerly Mineral Economics Division Established as a Division December 15, 1948 Established as a Council February 26, 1957 Franz R Dykstra, Chairman Paul Schultz, Vice-Chairman A J Phillips, Vice-Chairman Douglas Donald, Vice-Chairman J S Vanick, Contact AIME Director A H Lindley, Jr, Secretary-Treasurer Lehman Brothers 1 William Street New York 4, N Y COUNCIL OF EDUCATION OF AIME Formerly Mineral Industry Education Division Established as a Division January 15, 1932 Established as a Council February 26, 1957 0 Cutler Shepard,Chairman Lysle E Shaffer, Vice-Chairman John C Calhoun, Jr, Past Chairman J C Kinnear, Jr, Contact AIME Director J D Forrester, Secretary-Treasurer College of Mines Univ of Arizona Tucson, Arizona

Jan 1, 1958

By B. A. Wilcox

ThERE are several reports in the literature which indicate that both solid-solution hydrogen and hydride precipitates can promote low-temperature em-brittlement of tantalum.1-3 For example, Imgram et al.2 showed that hydrogen additions in the range of 140 to 580 ppm promoted a ductile-to-brittle transition at slightly above room temperature in both wrought and recrystallized tantalum. This contrasts with the observation that tantalum of norma1 purity is very ductile, even at liquid-nitrogen temperature. Imgram et al. also found that hydrogen additions caused a deterioration of notch tensile properties of tantalum. The purpose of this communication is to present some limited evidence that hydrogen can also cause fatigue embrittlement of tantalum. The material used in this investigation was wrought, stress-relieved (1000°C, 1 hr), are-melted tantalum rod (5/8-in. diameter) containing the following impurities in weight percent: 0.005 C, 0.007 02, 0.0005 H2, 0.003 N2, 0.08 Cb, 0.01 W, and 0.01 Fe. Hydrogen charging was done in an atmosphere of flowing dry hydrogen for 3 hr at 600°C, followed by an homogenizing anneal in purified argon for 15 min at 600°C, and cooling in an argon atmosphere. Typical micro-structures of the hydrogen-free and the hydrogen-charged materials are shown in Fig. 1(a) and Fig. 1(b), respectively. Fig. 1(b) shows the appearance of hydride precipitates which, in many cases, formed preferentially parallel to the rod axis. The hydride dispersion was uniform across the diameter of the specimen. The fact that the precipitate was a tantalum hydride was tentatively confirmed by X-ray diffraction on a metallographically prepared surface. After hydrogen charging, chemical analyses by vacuum fusion revealed the hydrogen content to be 0.0295 wt pct. In addition, the oxygen and nitrogen contents were slightly raised to 0.0095 O2 and 0.005 N2.

Jan 1, 1964

By D. G. Westlake

Levine has concluded that prismatic slip in titanium is controlled by two distinct thermally activated processes in the temperature ranges O° to 220°K and 220" to 300°K. We feel that his evidence is not convincing. He has drawn a curve through the plot of activation volume u* vs temperature T with a break at 22WK, Fig. 2. We believe that considering the possible experimental error apd the fact that there are only four points between 4° and 196°K, one could be justified to represent these points by the smooth curve we show as a solid line in Fig. 12. Levine believes that (8rf/aT)+ is discontinuous at 220°K, but he hints that he recognizes the possible doubt. We doubt seriously that the results shown in Fig. 1 indicate a discontinuity at 220°K. Certainly if he were justified in drawing a straight line through only four points on Fig. 2, we are even more justified in drawing straight lines through the seven points between 77" and 297°K on Figs. 1 and 3, because a straight line touches all seven of his circles. If his measurements of t were so precise that his decision to draw two curves in Fig. 3 is valid, then the experimental technique is deserving of further mention. We have drawn a smooth curve through the results in Fig. 3 and used this and the curve in Fig. 12 to obtain the values of shown in Fig. 13. Finding continuous is a contradiction of Fig. 4, which deserves comment itself. Levine obtained the solid circles in Fig. 4 using Fig. 2 and a smooth curve through the points shown in Fig. 3. We have replotted these solid circles in Fig. 14. We submit that there is no basis for his two straight lines (dashed in Fig. 14), and therefore have superimposed the curve that we believe is indicated. Certainly, there is reasonable doubt that a discontinuity in dH/dT exists at 220°K, even when one accepts Fig, 2. Furthermore, if one draws the straight lines indicated by least-squares treatments of the results presented as open circles in Fig. 4, their intersection is at about 196°K, not at 220°K as shown. Thus the alleged agreement between Figs. 3 and 4 with respect to "break" temperatures is not apparent. In Fig. 9, Levine has drawn a straight line very much different from the one indicated by a least-squares treatment. Obviously, he has done this because he recognized that H = 0 when T = 0. He is consistent in drawing the low-temperature curves in

Jan 1, 1968

By J. F. Shea, O. F. Tangel

Battelle Memorial Institute participated in a program for the General Services Administration aimed at developing a nickel-cobalt separation process that could be integrated in the Nicaro nickel plant. At the time the programwas being carried out, the Nicaro process was a straight-through operation, in which the ore was reduced and leached, after which the pregnant solution was boiled to produce a so-called "bulk precipitate" which contained virtually all of the nickel and cobalt which had been dissolved in the leaching step. The weight ratio of nickel to cobalt in Nicaro ore is approximately 15 to 20:l. The weight ratio of nickel to cobalt in the finished product had to be 100:l or higher to meet specifications. Because the Nicaro process embodied no nickel-cobalt separation step, the only way that a bulk precipitate of the specified nicke1:cobalt ratio could be produced was to so adjust roasting and leaching conditions that nickel would be selectively leached and most of the cobalt would be rejected with the tailings. The required selectivity, however, was achieved at the expense of nickel recovery, which was 5 or more per cent less than might have been obtained with the existing equipment, utilities, man power, etc., had selectivity been no object. The over-all purpose of the program was to develop a separation step that could be fitted into or onto the Nicaro facilities and which would permit the manufacture of a product that would meet the desired specifications and still permit the recovery of a maximum amount of nickel. Battelle suggested that this might be accomplished by reprocessing off-specification bulk precipitate and specifically suggested the process based on ammonium sulphate leaching followed by hydrogen reduction of the leach solution according to techniques developed commercially by Sherritt Gordon Mines Limited. Such a process would not only satisfy the objectives of the research but would present two additional advantages. (1) It would produce a separate cobalt product which could be further processed into metal, alloys, oxides, or salts. (2) It would yield nickel in metallic form which might be more generally marketable and command a slightly higher price per unit of nickel than the Nicaro oxide product. DESCRIPTION OF THE PROCESS Figure 1 is a flowsheet of the process. The essential features are: (1) Extraction of about 97 per cent of the nickel and about 85 per cent of the cobalt from bulk precipitate by a principal leach with ainmonium sulphate solution (Step A). Extraction of virtually all of

Jan 1, 1961

By K. K. Landes

The north central and northeastern states supply over 50 pct of the chemical and metallurgical limestone produced annually in the United States, and Ontario is the leading source of this material in Canada. About three fourths of the chemical and metallurgical stone produced in this area comes from Michigan, Pennsylvania, Ohio, and Ontario. The specifications, physical and especially chemical, for chemical and metallurgical stone depend upon the end use, but in general the tolerance for impurities is so low as to rule out most limestones and dolomites. Both high calcium limestone and dolomite are used in the metallurgical and chemical industries. The principal metallurgical use is as a flux in iron ore blast furnaces and open hearth steel furnaces. The major chemical uses are in lime burning and soda-ash manufacture. Other important uses include glass manufacture, in making calcium carbide, and in sugar factories. All deposits of high quality carbonate rock are definitely finite. Invariably and inevitably they diminish in either thickness or quality laterally so as to become unworkable as chemical and metallurgical stone. The size of these high quality lenses ranges from a few thousands of tons to hundreds of millions of tons. The best hunting for new supplies is in the geologic formations known to contain premium quality deposits. However, because of high transportation costs, carbonate rocks, to be workable, must be close to market, dollarwise. Definitions: Chemical stone is limestone or dolomite used as a raw material by the chemical industry. The major chemical uses are in lime burning and soda-ash manufacture. Other important uses include glass manufacture, making calcium carbide, and in sugar factories. The specifications for chemical stone depend entirely upon the end product. Some uses require dolomite, some require high calcium limestone; in a few instances, notably in lime burning, either type of carbonate rock can be used as raw material. As a general rule, a fairly pure stone is necessary and for certain particular uses the tolerance for some elements such as sulfur, iron, and phosphorus may be extremely small. Metallurgical stone is used as a flux in furnace operations, especially in the blast furnace where iron ore is converted into pig iron and in the open hearth furnace where pig iron is made into steel. Either limestone or dolomite can be used in the blast furnace, but only high calcium stone is charged in the open hearth (except for rice-size dolomite used as a refractory). There are no rigid chemical specifications for blast furnace stone, but low silica, alumina, sulfur, and phosphorus are desirable. For open hearth use, in addition to low magnesia, a very low sulfur content is also specified by many furnace operators. For furnace use, fluxstone also must be sufficiently shatter resistant that it will remain in lump form during transport and charging into the furnace. Commercial stone is the term applied in the trade for crushed stone used for roadstone and in concrete aggregate. Many of our best chemical and metallurgical limestones are too soft to qualify in the Los Angeles abrasion test for use as commercial stone. However, some limestones, and a higher proportion of dolomites, do qualify for commercial stone and so can be sold to either market. Place Value: Even the highest grade limestone is still a bulk commodity with a relatively low value per ton. As a matter of fact there is very little difference in the average price per ton between high grade chemical and metallurgical stone and crushed limestone used commercially. Most high quality stone is produced in large operations with consequent low cost per ton whereas most commercial stone is produced in relatively small local quarries. As in the case of other bulk commodities most limestone buyers pay more for transporting the raw material than the cost of the stone at its source. For this reason steel furnaces and chemical plants

Jan 1, 1961

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors' conclusion.

Jan 1, 1968