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By R. S. Rickard

Using a simple model, the necessary chemical conditions for sulfide leaching will be discussed. Also other chemical control- ling factors will be reviewed briefly.

Jan 1, 1974

By C. E. Sims, H. M. Banta, S. L. Hoyt

OVER the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking specifically underbead cracking, or "hard cracks," or parent-metal cracks-is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.1 The tests described are made under restraint to facilitate cracking and, are so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when arc-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking. tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institute 0n two projects, one

Jan 1, 1945

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By Lyden, Joseph P.

THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.- This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications.

Jan 1, 1950

Jan 1, 1900

By Joseph L. Mehaffey

A variety of chemicals offered by Armak were evaluated as dewatering aids for aqueous slurries of silica sand, sparsand and feldspar; an established commercial dewatering aid was used as a control. A number of Armak’s potential dewatering aids yielded lower moisture retention values than did the commercial product on all of the mineral samples. In addition to the chemical dewatering evaluations, some of the mechanisms involved in the removal of water from these mineral samples were examined.

Jan 1, 1984

By Franklin H. Sharp

The operation of the Magmont Concentrator located on the New Lead Belt of Southeast Missouri is described. Ore characteristics affecting lead-copper-zinc separation are enumerated, and the cur- rent methods of separation are detailed.

Jan 1, 1976

By John H. Puffer, Andreas H. Vassiliou

The Bemco mine area is within the Precambrian igneous and metamorphic rock terrain of the New Jersey Highlands province. Rocks In the area include a pyroxene granite, a hornblende granite, a quartz-oligoclase gneiss and a pegmatite and its host rock, a lens of amphibolite which becomes a sulfide-rich pyroxenite near the ore zone. The ore-bearing zone occurs along the hanging wall and foot-wall contact of the pegmatite which was emplaced discordantly into the amphibolite-pyroxenite.

Jan 1, 1985

Jan 1, 1941

By Robert T. Hill

PHYSIOGRAPHICALLY, Mexico provinces, which are, in a manner, distinct economic areas. These may be denominated, (1) the Gulf coastal plain; (2) the Cordilleran plateau; (3) the Sonoran, and (4) the Tehuantepecan province. Fig. 1 shows the approximate boundaries of these provinces. The first is the continuation of the coastal plain of Texas and the Gulf region in general, which, except for prospective oil and lignite, has little of interest for the mining engineer.

Jan 1, 1902

By M. W. Burkart, B. Lustman

Uranium-base alloys exposed to high temperature water fail either by uniform oxidation or by sudden cracking and disintegration of the metal. The disintegration results from the oxidation of a second phase which is precipitated during the corrosion process. The precipitate has been identified as a metastable hydride of uranium. URANIUM-BASE alloys consisting of the body-centered-cubic ? phase are susceptible to two different modes of corrosion failure when exposed to high temperature water. In the first process, a smooth oxide film is formed on the metal surface which continually flakes off during exposure and results in a uniform weight loss of the specimen. The oxide is present as a thin, adherent layer whose thickness remains approximately constant. As the metal oxidizes during corrosion, a nonadherent layer is built up on this film and continually sloughs off. Coincident with the uniform corrosion just mentioned, another process occurs which eventually leads to failure of the metal by cracking and general disintegration. The failure takes place during a relatively short time compared to the total exposure. To distinguish this type of failure from the uniform corrosion, the cracking or disintegration of the metal will be referred to as discontinuous failure. For the ? phase uranium alloys it is discontinuous failure rather than uniform corrosion that limits the useful corrosion life of the alloy. This paper will be concerned primarily with the mechanism of discontinuous failure. Physical Changes During Corrosion—The alloys used in this investigation were ? phase uranium alloys containing 7 to 12 wt pet Mo or Cb. The preparation of the alloys, the method of corrosion testing, and the actual corrosion results are presented in another paper.' The ? quenching treatment consists of annealing the alloy for 24 hr at 900°C in a sealed Vycor glass tube filled with helium and then water quenching to room temperature without breaking the tube. The corrosion behavior typical of a ? phase uranium alloy is shown in Fig. 1. This specimen was a U-12 wt pet Mo alloy tested in pressurized, degassed water at 650°F. The corrosion rate was practically constant at 0.28 mg per sq cm per hr or increased slightly until about 15 to 20 days of exposure, when the onset of discontinuous failure occurred in this particular sample, and the specimen soon began to crack and disintegrate. The simultaneous increase in the observed corrosion rate is a result of the increased area of exposure due to cracking of the specimen. The microstructure of a specimen that failed by cracking is shown in Fig. 2. The presence of a plate-like precipitate can readily be seen. Metallographic examination of corrosion specimens reveals that the onset of discontinuous failure is always preceded by the formation of a plate-like second phase in the ? uranium matrix. Hydrogen analyses of specimens periodically withdrawn from corrosion test reveal that the hydrogen content of the alloy increases on exposure to the high temperature water, as shown in Fig. 3. The hydrogen is available as a corrosion product resulting from the formation of UO2 by the reaction of the alloy with water. Specimens analyzed just prior to discontinuous failure contained as much as 1200 ppm H, whereas the plate-like phase appears to precipitate out at a hydrogen concentration of between 10 and 25 ppm. The observed increase in hydrogen content prior to and during the formation of the plate-like precipitate suggests that this constituent may be a hydride of uranium. Additional evidence linking the identity of this phase to a hydride is that it can be removed by vacuum annealing at temperatures of 100°C and above. Decomposition products of the ? phase would certainly not dissolve at such temperatures, nor could other likely products of corrosion, such as oxides, be dissipated at any of the test temperatures. The precipitation and growth of the second phase during corrosion is accompanied by an increase in hardness of the specimen. The hardness increase results from the dispersion of the harder precipitated

Jan 1, 1959

By C. B. Manula, R. Venkataramani

Application of computers to present-day open-pit mining with bucket wheel excavators (BWE) is discussed. The development of the wheel excavators and their use in mining are discussed along with the necessity for building a computer model of the bucket wheel and the mathematical formulation of the problem. The simulation procedure, testing the model, and test results are summarized. Even though the mining industry in 1966 produced more ore than ever before, current extraction rates are only a fraction of what is expected in the later years of the 20th century. Nearly 90% of all metals and mineral products consumed last year was recovered by open-pit mining. This has placed great pressure on this segment of the industry which has, consequently, resulted in some spectacular developments. With increasing size of projects, the need for increased sophistication of engineering, planning, management, and administration of modern mining installations has never become more apparent. The design of complete systems for the mine and plant that fit the mold of today's business and social environments is undergoing an evolutionary process. Traditional concepts in mine development and operations are being sidestepped in favor of new ideas and principles. As the overburden thickness increases, materials handling presents a major problem to mining companies, especially those concerned with the mass production of ore and waste from low-grade deposits. The profit margin here is likely to be significantly less as to take chances with capital investment. Constant efforts are needed to improve upon productivity if the ore is to be economically mined. The development of vast low-grade deposits and thick overburden deposits calls for better tools to handle the enormous amount of materials. A natural solution to this problem is the use of bucket wheel excavators (BWE), which employ a continuous cutting head to feed the materials handling system. High productivity, versatility, economy of operation, and adaptability to most types of haulage systems combine to make BWE's attractive for large earth-moving operations. "Operating costs are being pushed down by the impact of giant haulage units, by high-speed conveyors, and computerized railroads. Matching all these with the continuous output of BWEs, one can visualize increased production at much lower costs." Historical Background The wheel excavator, which was patented in Germany in 1913, made its first appearance in an open-pit lignite mine in 1920. From this early beginning, however, BWEs were slow coming into practice. Initial developments were dampened by many design problems. From 1936 onward, major developments in design improved the wheel's ability, capacity, and versatility. A literature survey shows that wheel excavators are being used in Australia, Zambia, South Africa, the Congo, India, Indonesia, Czechoslovakia, Russia, Great Britain, Guyana, Yugoslavia, Morocco, Germany, Canada, and the U.S. for mining and loading chalk, lignite, clay, sandstone, phosphate, broken ore of iron, coal, shale, loose and semi-loose rock overburden.' A recent LMG* BWE at work in a German lignite mine weighs 6790 tons with an hourly capacity of 11,000 cu m. Although the BWE has wide applicability, its application to new mining areas poses a problem. Because of the large capital investment involved in BWE application and the narrow profit margins in mining low-grade ores or coal at depth, little margin of error can be tolerated in the selection, design, and operation of these machines. The questions that need to be answered prior to installation of a BWE for a mineable deposit are: 1.) What are the anticipated BWE performance characteristics? 2) Which method of BWE operation is most efficient? Attempts to answer these questions require a thorough knowledge of the mining system and the BWE operation. One approach is the building of a computer-ori-ented simulation model to determine how information and policy create the character of the BWE system under consideration. BWE Operation Modern BWEs generally excavate in blocks. Fig. la shows a BWE working in an established cut. The wheel is positioned to travel on the pit floor in line with the top edge of the old highwall. As it advances, a new highwall is exposed in the direction of excavation. Digging is done by rotating the wheel, swinging it from side to side in long parallel arcs, and "crowding" into the bank, by advancing the entire machine, or by the travel of the digging boom if an automatic crowd is available (Fig. lb). A second way by which the wheel can be advanced into the bank is by the falling cut method. A brief description of each of these methods follows. Cut with a Crowding Machine: At the end of every swing, the digging boom can be extended by the thickness of cut desired and the boom swung back in the reverse direction. Obviously, the thickness of bank excavated does not vary with the boom position; therefore, the slewing motion of the boom is fairly constant for uniform output. The thickness through which the digging boom can be advanced into the bank is theoretically calculated from the formula'

Jan 1, 1971

CHEMICAL PRECIPITATION U.S. 4,067,789 - Removal of soluble manganous ions from a zinc sulfate solution formed by leaching roasted zinc sulfide ore with spent electrolyte. An excess of ammonium persulfate or like oxidant is added to the leach solution to convert manganese to insoluble, filterable gamma-manganese dioxide, and the precipitate separated from the solution by filtration. L. Harris and A. K. Hanson, Jr., assigned to Newmont Exploration Ltd. Jan. 10, 1978. 11 pp. (204-119). Filed: 5-3-76 (682.442). (Drawing on page 67.)

Jan 1, 1979

By George I. Smith

Jan 1, 1985

By W. A. Backofen, M. L. Ebner

SINCE the early work of Gough with Hanson and Wright,l-3 the study of fatigue has been characterized by experiments on single crystals only in recent times.9-10 Now, increasing attention is given to this aspect of fatigue research for the insight that it may provide into details of mechanism. The investigations have concentrated to a large extent on the development of deformation markings on fatigued crystals, and have shown the cracks to originate in slip bands possibly preceded or accompanied by slip-band extrusions. Experiments of special interest to the present work were conducted by paterson5 on copper crystals and involved both metallographic examination and measurement of change in flow stress. Crystals were cycled in alternating tens ion-compress ion with a constant plastic shear-strain amplitude of approximately 0.8 pct, and were particularly revealing for their demonstration of hardening with accumulated strain similar to that in unidirectional straining, through an easy-glide stage I followed by a stage II of rapid hardening; deformation was not continued beyond 40 cycles, however, so that the eventual course of the hardening curve could not be decided. For the conditions used by Paterson, surface slip markings were similar to those observed in unidirectional straining, but there were no X-ray asterisms and no deformation bands on the surface. In current thinking about the nature of fracture in fatigue, two views relative to mechanism are generally acknowledged, with the reservation that both could apply simultaneously in some measure. As one possibility, fracturing across a slip plane is regarded as a result of loss of cohesion from the creation of many point defects by dislocation movement under the cyclic loading.'' On the other hand, fracture has also been taken to follow as a consequence only of the geometry of slip at a free surface, consisting of offsets and crevices which eventually become fatigue cracks.12, l3 The work of McCammon and Rosenbergl4 showing fatigue in polycrystals at 4.2oK makes clear that any long-range diffusion of point defects is unnecessary, yet studies such as those of Forsyth and stubington15 show that accelerated diffusion may be a characteristic of deformation under fatigue loading. Interest in obtaining data of possible use for resolving such questions led to the experiments described below. Copper crystals were conveniently loaded in alternating four-point bending at constant deflection, a test condition shown to approximate a constant plastic strain amplitude for a wide range of axial orientations. The method of testing was not readily adapted to extensive study of temperature effects, but an investigation of the geometry of crack formation could simply be made by orienting,the slip direction at different angles to the surface. EXPERIMENTAL PROCEDURES Single crystals were grown by a modified Bridgman method in a stationary gradient furnace under an atmosphere of purified dry nitrogen. Purity of as-grown crystals was 99.999 pct as determined by spectrographic analysis plus vacuum fusion and gravimetric analyses for oxygen and sulfur, respectively. Crystals were of reasonable perfection as evidenced by a critical resolved shear stress at 10 deg from (110) of 60 g per sq mm and half-width of a (400) X-ray diffraction line from one crystal of

Jan 1, 1960

By Tokio Yanagida

Major parameters relating to the operating of the conventional calcine-charged reverberatory f'ce process such as distribution coefficients of major elements among slag, matte, blister, and gases, temperatures and weights of intermediates, and heat losses of furnaces were measured and determined. A computer program to estimate heat and material balances at the process was prepared utilizing these data, showing a good agreement with actual results.

Jan 1, 1984

By T. W. Healy, D. R. Dixon

The mechanism of activation of ZnS by metal ions and the subsequent flotation induced by xanthate has been considered as a surface redox reaction. By ultraviolet (UV) irradiation of ZnS suspensions, the normally inert ZnS is caused to react with xanthate in the absence of activator. By similar UV irradiation, the rate of adsorption-exchange of activator ions at the ZnS-H2O interface is also increased. Mechanisms of these reactions are proposed and compared to current electrochemical and semiconducting models of sulfide flotation.

Jan 1, 1976

By B. A. Wilcox, A. H. Clauer

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys&apos;10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

Jan 1, 1941