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By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By H. W. Weart, S. Sarian

The effect of temperature, impurities, and capillarity on the morphology of solid particles in a liquid matrix is investigated. For the NbC-liquid iron system, at least, it is found that those particles which are dissolving will assume a spherical shape; all others will take the equilibrium shape. An aniso-tropic-isotropic transition in the interfacial tension is observed at about 1725°C and is believed to be due to cooperative roughening of the interface on an atomic scale. The presence of boron as an impurity lowers the transition temperature. It is the purpose of this paper to present some observations on the shape of particles in a system consisting of solid particles of nonuniform size in a liquid matrix and to propose an explanation for these observations. Although qualitative only, these observations, which were made largely in the course of a study of particle-growth kinetics,' are presented separately to draw attention to them. They reveal the effect of particle size, temperature, and surface-active impurities on particle shape in the solid NbC-liquid iron system, and are unique in demonstrating for the first time the reversible effect of temperature and impurity concentration on the anisotropy of the energy of the solid-liquid interfaces involved. Some of the changes are readily demonstrated with the few particles whose shapes can be clearly shown in a single photomicrograph, but others are more subtle, and their recognition depends upon some experience and the study of a much larger sample. For this reason, a certain amount of judgment must be acknowledged to underlie their detection, but every effort was made to maintain proper scientific objectivity in evaluating the observations. The observations will be presented first, and then an explanation rationalizing them will be offered. Brief reminders of the relevant theories will be inserted into the discussion at the appropriate points. EXPERIMENTAL The observations were made of the shape of NbC particles dispersed in liquid iron. All specimens were prepared by pressing NbC powder and car- bony1 iron powder treated according to standard powder-metallurgical procedures. Except as noted, all specimens were heated to 1900°C for 1/2 hr. In investigating the effect of temperature, specimens were quenched from 1900°C to various lower temperatures, and held long enough (48 hr) to allow shape changes to be completed. Boron, in the form of amorphous powder, and oxygen, in the form of niobium oxide powder, were added as impurities to some specimens. Nitrogen was introduced into some specimens as an impurity by heat treating the samples under a partial pressure of nitrogen gas. Effect of Temperature. It was first observed that increasing temperature had a marked effect in rounding the corners and edges of the particles. At 1900°C the particles are all very nearly spherical and remain so even when the holding time is extended to 48 hr. As can be seen from Fig. 1, there is virtually no evidence of the presence of low-index planes. At 1300°C, however, most of the particles are prismatic with very slightly rounded edges and corners, Fig. 2. (In making these shape comparisons, attention should be focused on the larger particles, even though the smaller ones would be expected to be the first to change shape, owing to the shorter diffusion distances involved. The cause of the mixed particle shape will be explored later.) It was established that these structures are re-

Jan 1, 1965

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By G. P. Walters, W. C. Fuller

THE production of thin films of beryllium became essential early in the irradiation program at Harwell in order to study the fundamentals of irradiation damage in this metal. In common with other metals, electron-microacope specimens of beryllium can be produced by different techniques. The techniques used to produce thin-film specimens varied according to the starting material. Most of the starting material was -0.060 in. thick. Large-area specimens (1 in. long by 0.5 in. wide) were chemically thinned to -0.005 in. thick in a solution containing 85 pct orthophosphoric acid, 10 pct chromium trioxide, and 5 pct sulfuric acid at 70°C prior to electropolishing. Small-area specimens, Fig. 1, had to be mechanically thinned prior to electropolishing because chemical thinning considerably reduces the area as well as the thickness. Mechanical thinning tends to produce a worked layer about 0.002 in. deep and hence this method cannot be used to thin bulk specimens below about 0.005 in. thick. Mechanical thinning is carried out by mounting the specimen on perspex then carefully polishing on wet grinding papers. Polishing is continued until about half the initial thickness is removed; the reverse side is then polished in a similar manner. After the bulk specimens have been mechanically or chemically thinned to -0.005 in. they are elec-tropolished in the solution shown in able I at 50" to 80°C. This solution should be prepared by adding the chromium trioxide to the orthophosphoric acid and then the glycerol last. The glycerol should be added slowly because a vigorous effervescence can occur. Electropolishing is carried out by holding the specimen in stainless-steel tweezers and gently agitating in the solution. Masking or "window" techniques are not required for beryllium, good microscope specimens being obtained from the edges of elec-tropolished foils. A stainless-steel beaker should be used, acting as the cathode and solution container. A closed circuit voltage of 30 v is used for polishing. Too low a voltage produces a matt surface and pitting occurs when it is too high. The solution temperature is important. If it is too low, the solution is viscous and bad polishing results and, if too high, etching of the specimen occurs. After electropolishing, the foils are thoroughly

Jan 1, 1963

By R. H. Frazier, F. W. Boulger

THE performance of welded structures is closely associated with the ductile-to-brittle transition temperature of the steel from which they are made. A low transition temperature is desirable because it indicates that the steel is less likely to fail suddenly at low ambient temperatures. Structures such as bridges, ships, storage tanks, and pipelines are usually made from hot rolled semikilled steel. Changes in rolling practice or chemical composition appear to be the most practical methods for improving the toughness of such materials. This results from the fact that production is likely to be seriously curtailed if improvements were obtained by recourse to heat treatment or complete deoxidation. This paper discusses the effect of variations in carbon and manganese contents on the properties of semikilled steels. The transition temperature, a property to which considerable importance is attached, varies with specimen configuration, testing method, and criterion of performance. Both the Navy tear test' and the keyhole Charpy test were used in the investigation. According to the terms used by Vanderbeck and Gensamer,V he tear test was used to measure a fracture transition and the Charpy test to measure a ductility transition. In either case the specimens absorb considerably less breaking energy in tests below the transition temperature than in tests above the transition temperature. Decreasing the testing temperature of notched-bar specimens seems to be equivalent in its effect to increasing the severity of loading on fabricated structures. Therefore, structures built from steels exhibiting lower transition temperatures in laboratory tests are expected to be less susceptible to sudden brittle fractures in service. Consequently, changes in composition which lowered the transition temperature of the experimental steels were judged desirable. Materials and Methods The steels for this study were made in a laboratory induction furnace and rolled to 3/4 in. plate, using a finishing temperature of 1850°F. Precautions taken to insure reproducible melting and testing practices are discussed in detail elsewhere.' All tests were made on hot rolled steels. The analyses of the experimental steels are given in Table I. The list includes steels with manganese contents ranging from 0.21 to 1.46 pct, at each of five carbon levels. The phosphorus, silicon, sulphur, and nitrogen contents of the steels are reasonably constant. The tensile and notched-bar properties of the experimental steels are presented in Table 11. Both upper and lower yield points are listed, and all values are averages for duplicate specimens. Transition temperatures based on three criteria are given. The keyhole Charpy transition temperatures are the temperatures at which the energy-temperature curves based on averages of four specimens cross the 20 and 12 ft-lb levels. Both definitions of Charpy transition temperatures have been used by other investigators. Charpy tests were made at intervals of 10°F, using a pendulum with an available striking energy of 220 ft-lb and a velocity of 18.1 ft per sec. The specimens were oriented parallel to the rolling direction and notched normal to the surface of the plates. The tear test transition temperatures are based on the usual' criterion of the highest temperature at which at least one of four specimens exhibits brittle behavior. The dimensions of the tear test specimens are shown in Fig. 1. The specimen is loaded eccentrically in tension, with pin and shackle fixtures, through the large holes while submerged in a liquid bath at the proper temperature. A specimen developing a fracture area with less than 50 pct shear or ductile texture is classed as brittle. Tear tests were made at intervals of 10°F.

Jan 1, 1955

By R. Adair, W. R. Hudspeth, W. T. McDaniel

ANEW method for concentrating the flake mica either from present washing plant tailings or from new feed has been developed. In this paper, flake mica refers to that which occurs in weathered granites, alaskites, pegmatites, and schists in a form too fine to be considered sheet mica. It ranges in size from 1 in. or more down to 200-mesh or finer and occurs with kaolin, quartz, and partially kaolinized feldspar. Scrap mica, a term often used indiscriminately to describe everything other than sheet mica, will be used to denote the waste product from sheet mica mines and fabricating plants. Both flake and scrap mica are used in the mica grinding plants to produce wet-ground or dry-ground mica, although some flake mica recovered from clay mining operations is fine enough to be marketed without grinding. Until 1930, ground mica was made almost entirely from scrap. From 1930 until 1935 a gradually increasing amount of flake mica was mined, and most of this was sold without grinding. A large percentage of this mica was recovered from clay washing plants. In this type of operation the recovery of any sheet mica was .of secondary importance and was considered a byproduct. North Carolina produces more flake mica than any other state, accounting for 73 pct of the total domestic production.' In the following review of current practice in jig plants, there is no intention to disparage these operations. Within the limitations under which they were built, they are examples of mechanical ingenuity. The term jig plant is a carryover from early practice since there are no jigs in operation at the present time. Current practice, as shown in Fig. 1, is based on successive stages of differential crushing with rolls followed by trommel screens to remove the more easily crushed gangue minerals. The oversize mica product then is usually dried, and passed through another set of dry rolls and a final screen to remove the remainder of the grit. This process is effective in recovering up to 50 pct of the mica in the original ore, the balance being lost in the screen undersize, usually —% in. Jigs and tables were at one time used to treat this screen undersize and were capable of recovering a part of the mica larger than about 60-mesh.V ine mica lost in these plants is normally washed away in streams and can be considered irrecoverable. There are ten or more washing plants in the North Carolina area that are losing approximately 50 pct of the mica in the feed. Since the three cooperating agencies, the Asheville Minerals Research Laboratory of North Carolina State College, the North Carolina Dept. of Conservation and Development, and the Tennessee Valley Authority, are concerned with conservation of minerals, they have investigated means for improving the efficiency of these mica plants. The mica industry has been cooperating fully with the laboratory to establish a more efficient method of recovery for flake mica. Choice of Methods The initial investigation was concentrated on finding a means of reducing the losses from plants now using the conventional flowsheet shown in Fig. 1. To accomplish this it would be necessary to collect the screen undersize products through the plant and remove from them the mica from Vs in. down to

Jan 1, 1952

PHILIP D. WILSON,* Warren, Ariz. (written discussiont).-Mr. Tovote's idea of attempting to classify according to their broad geologic relations the ore deposits and prospects of the Southwest is an admirable one. Attempts have been made to evolve some comprehensive scheme of classification that would be of practical assistance in determining the possible value of prospects, but the ore deposits are too varied in type, form, genesis, and distribution to lend themselves readily to any definite, scientific pigeon-holing. The classification Mr. Tovote recommends, combining the age of the mineralization with the type of the rock supposed to be its source, is open to criticism even on the evidence he presents. The age of many deposits is not nor can be definitely determined because of the absence of sedimentary rocks in their vicinity. Furthermore, the character of the mineralizing solutions has, in a large majority of cases, no relation to the composition of the associated igneous rock. While the solutions may have originated in the same magma, they were usually a much later manifestation of it, often appearing after the intrusive rock had completely solidified and been subsequently crushed and fractured, and in many cases the chemical difference is very marked. It is true that igneous activity in the Southwest is definitely related to-certain geologic periods. The statement, however, that no ore deposits can unmistakably be referred to periods earlier than late Cretaceous is not supported by fact. The bonanza copper orebodies of the Jerome District are definitely pre-Cambrian. As suggested by J. R. Finlay,1 they are probably post-Beltian or late Algonkian in age, perhaps related to the same great mountain-making period as the copper deposits in the Keweenawan series of Lake Superior and the Sudbury, Porcupine, and Cobalt deposits of Ontario. The proof that they are pre-Paleozoic may be summarized as follows: 1. The pre-Cambrian complex in which they occur is overlaid by a great thickness of Paleozoic sediments with the Tonto or Tapeats sandstone at their base. The only primary mineralization in these sediments is an economically unimportant one connected with very recent basalt. 2. In the United Verde Extension mine, the gossan over the great orebody extends to the old pre-Cambrian surface where it is directly

Jan 2, 1919

By Klaus M. Zeitler

INTRODUCTION One cannot discuss the subject of "Raising Capital in the 1990s" without having a crystal ball and a reliable fortune teller. This discusses "Raising Capital for the 1990sW, which is what Metal1 Mining Corporation did in 1987. We raised (3166 million in an IPO (initial public offering) that was originally planned for only some (375 million. Why did we raise this money? How did we do it, and why was this IPO so successful? The answer to the first question requires a description of the promoter and principal shareholder of Metal1 Mining Corporation, Metallgesellschaft AG. This West Germany company was founded over 100 years ago in Frankfurt as a trading house for non-ferrous metals. It has developed into one of the world's leading firms in the non-ferrous metals industry. The company's worldwide activities in all areas of that business include mining, smelting and refining, the trading of ore, base and precious metals, the production of semi-fabricated and finished metal products, and the provision of engineering, construction and transportation services. Metallgesellschaft AG has also diversified into many other areas, the most significant of which are manufacturing, the production of chemicals, the development and application of technical and chemical processes, the planning and construction of industrial plants, and activities associated with finance, insurance, shipping and freight forwarding, and the provision of barter and countertrade services. The company maintains a network of more than 100 offices around the world; it employs some 25,000 people in its worldwide activities. [Selected financial data, as of September 30, 1987: (MetaUgesellschafl AG) Working Capital DM 8%.6 million CDNS 672.8 million Long Term Debt DM 568.0 million CDNS 426.2 million Sales DM 14.9 billion CDNS 11.2 billion Net Income DM 87.7 million CDN$ 65.8 million Market Capitalization at April 27, 1987: (Metallgesellschafi AG) Outstanding Shares ~,6oo,o0o DM 1,875 million CDNS 1,407 million] For the fiscal year ended September 30, 1987, Metallgesellschaft AG had, on a consolidated basis, net sales of DM13.3 billion, net income of DM100 million and total assets of about DM7.0 billion. Metallgesellschaft AG established the American Metal Company, a predecessor of AMAX Inc. one of the largest ventures undertaken by Metallgesellschaft AG then was the acquisition, through the American Metal Company, of a majority share in the Mexican Penoles mine, a large lead and silver deposit. METALLGESELLSCHAFT AG Figure 1 depicts an overview of Metallgesellschaft AG before and at the time the initial public offering of Metall Mining Corporation's shares took place. It shows that mining was far from the centre of Metallgesellschaft's activities. Therefore, it could not expect to receive an extraordinary amount of board attention. Thus, mining investments not only had to compare well with other mining opportunities, but were in fierce competition with projects from other divisions. In addition, mining was sub-divided into two separate departments -- domestic and international. These two departments had different management styles and diverging interests which resulted in a minimum co-operation between them. The domestic mining department was primarily interested in the survival of the local mines. These mines were characterized by rising operating costs and declining ore grades. It took a special commitment and continued ingenuity to develop and adjust to local conditions, and modern mining and processing technology, in order to remain competitive, or at least survive within the international mining industry. Local management

Jan 1, 1990

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By Mark J. Klein

The creep of 043 was studied over the temperature range 1650" to 3200°F and over the stress range 3000 to 44,000 psi. The steady-state creep rate over this range of stress and temperature can be expressed by the equation where A is a constant, is the stress, and is -0.8 x 103 psi-'. Over a narrow range of stress variations c0 a and for this proportionality n varies from 3 to 30 in accordance with the relation n = aB. Above about 2400° F, H, the apparent activation energy for creep, is 110,000 cal per mole, a value about equal to that estimated for self-diffusion in this alloy. Below 2400°F, H increases with decreasing temperature reaching a value of -125,000 cal per mole at 1700° F. In this temperature region, H appears to be a function of the interstitial concentration of the alloy. MOST of the detailed creep studies of dispersion strengthened metals have been concerned with metals having fcc structures. However, there are a number of important refractory alloys with bcc structures that derive part of their high temperature strength from an interstitial phase and whose creep behavior has not been well defined. This paper describes the creep behavior of the bcc alloy, D43, over the temperature range 1650" to 3200°F (0.4 to 0.7 Thm) and over the stress range 3000 to 44,000 psi. In addition to colum-bium, this alloy contains 10 pct W. 1 pct Zr, and sufficient carbon (-0.1 pct) to form a carbide dispersion throughout the matrix of the alloy. The effects of variations in temperature and stress on the steady-state creep rate of this alloy are presented in this paper. EXPERIMENTAL PROCEDURES Creep tests were made in a vacuum of 106 torr under constant tensile stress conditions using a Full-man-type lever arm.' Creep specimens were machined from 0.020-in. D43 sheet (grain size -5 x l0-4 in.) processed in a duplex condition (solution annealed -2900°F, 40 pct reduction in area, aged 2600°F). The specimens were tested in this condition without further heat treatment. Specimen extensions over 1-in. gage lengths were continuously recorded using a high temperature strain gage extensometer. Differential temperature and stress measurements were used to determine temperature and stress dependencies of the creep rate. Activation energies were calculated from the changes in strain rate induced by abrupt shifts in the temperature during constant stress creep tests. The 100°F temperature shifts used in most of the activation energy determinations required 15 to 90 sec depending upon the temperature at which the shift was made. The dependence of strain rate on stress was determined by measuring the change in strain rate for incremental stress reductions during constant temperature tests. It has been shown that columbium-base alloys such as D43 are susceptible to contamination by gaseous interstitial elements during vacuum heat treatments.' In this regard, it is unlikely that these alloys can be heat treated without some loss or gain of interstitial elements despite the precautions taken to control the heat treating environment. However, several factors suggest that changes in interstitial concentrations of the specimens during testing did not affect the results presented in this paper. First, the dependence of the creep rate on the stress or temperature determined during the course of a single creep test showed no variations with the duration of the test. A variation would be expected if a loss or gain in interstitial concentration during the course of the test affected results. In addition, precautions taken during this investigation to minimize interstitial contamination by wrapping the gage lengths of the specimens with various foils2 (Mo, Ta, W) did not produce a detectable change in the stress and temperature dependencies relative to the unwrapped specimens. The averages of duplicate analyses for carbon and oxygen in several specimens determined before and after creep testing are listed in Table I. The combined nitrogen and hydrogen concentrations which were ordinarily less than 50 ppm did not change in a detectable way with creep testing. The analyses show that only minor changes in carbon concentration occurred during creep testing except for specimen 4. This specimen which was tested at 3100°F lost a significant amount of its carbon concentration to the vacuum environment. Specimen 1 gained 100 ppm of O, while specimens 2, 3, and 4, which were tested at progressively higher temperatures, lost increasing portions of their initial oxygen concentrations during testing. RESULTS AND DISCUSSION The Temperature Dependence of the Creep Rate. The apparent activation energy for creep, H, was de-rived from creep curves similar to that shown in Fig. 1. Steady-state creep was rapidly attained at the beginning of the test and with each change in temperature. This behavior suggests that the alloy rapidly attains a stable structure with each shift in temperature or that the structure is constant throughout the test. Since the dispersion will tend to stabilize the structure, the latter is probably the case. The activation energy was found to be independent of the direction of the temperature shift and the magnitude of the shift (50" or 100°F). Although H was approximately independent of the strain, there was a tendency for it

Jan 1, 1970

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.' Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

WM. A. COWAN, Brooklyn, N. Y. (written discussion*). -This is evidently an excellent continuation of the work described in the article "An Investigation of Fusible Tin Boiler Plugs" by Messrs. Burgess and Merica.1 The present paper gives information of much value in con-nection with the manufacture and inspection of fusible boiler plugs, and the investigation of the cooling curves of tin with various other metals close to the tin side of the diagram is very interesting. These curves corroborate in all cases, except that of antimony, the diagrams given by other investigators. However, only the liquidus curves of the thermal equilibrium diagrams are given, except for copper-tin alloys where one branch only of the solidus (representing the freezing, of the eutectic)

Jan 11, 1919

By Ernest R. Dickie

IN 1945 the Bagdad Copper Corp. decided to change from block caving to open-pit mining. By early 1948 the conversion was completed and production was increased from 1500 tons per day to 4000 tons per day. Open-pit mining costs decreased approximately 40 pet from the cost of producing ore by the underground method. At present one P & H model 1400 all-electric 4 1/2-yd shovel and one P & H model 1055 Diesel 3-yd shovel are used continuously for stripping. One 21/2yd North- west shovel handles the ore. Delivery of a new P & H 1055 electric shovel for stripping is expected this month. Blasthole drilling is performed with two Bucyrus model 22 and two Bucyrus model 27 churn drills.

Jan 9, 1951

By Sven Fornander

L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author's reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952

By AIME AIME

IN view of the approaching visit to Japan and the Imperial Steel Works at Yawata by our members, the following notes on present conditions in the industry there will be of interest. The data were collected by the representatives of the Bureau of Foreign and Domestic Commerce in Japan and are furnished here through the courtesy of the Department. In connection with the proposed suspension of both new and old Government undertakings and the general depression in building, which is expected to result from the retrenchment policy of the Government, some cuts in iron and steel prices have been made by dealers. It is expected that the Yawata Steel Works may reduce its round bar prices for November delivery by 1 yen.

Jan 1, 1929

By AIME AIME

THE Petroleum Division held a very successful meeting in Los Angeles, Oct. 4 and 5. The meeting was held on the eighth floor of the Chamber of Commerce building, the first day being devoted to technical sessions. Seventy-five members were registered before the opening of the first session. Glenn D. Robertson, vice-chairman of the local section, opened the meeting and introduced Edwin Higgins, managing director of the California Oil and Gas Association, who gave an interesting talk on the recently enacted gas conservation law in California. He explained that the law is an experiment which will be watched with a great deal of interest. The purpose of the law, which went into effect on Sept. 1, is to curb wastage and over-production of gas,

Jan 1, 1929

By Horace C. Knerr

It has been shown that the resistance to corrosion of duralumin sheet is greatly influenced by the quenching medium used in heat treatment, or, more specifically, by the rate of cooling during quenching. The severity of corrosive attack after exposure to salt-water spray increases in .the following order: The tensile strength, yield point and elongation are only slightly affected by the quenching medium, as shown in Table 1. Tensile test requirements: yield stress, 25,000 lb. per sq. in. minimum; ultimate stress, 55,000 lb. per sq. in. minimum; elongation in 2 in., 18 per cent. minimum.

Jan 1, 1931

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. Development of the new units was prompted by a desire for solution of the following problems: 1—The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pct of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be pro- vided in the event that air lines were no longer available. 2—Drill performance has increased beyond the capacity of present 3-in. drifter machines. 3—The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4—Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5—Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6—In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1—It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1953

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. Development of the new units was prompted by a desire for solution of the following problems: 1—The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pct of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be pro- vided in the event that air lines were no longer available. 2—Drill performance has increased beyond the capacity of present 3-in. drifter machines. 3—The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4—Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5—Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6—In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1—It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1953