Search Documents

By C. A. Eligwe, F. W. DeVries, A. E. Torma

This study is an investigation on using hydrogen peroxide for tank-leaching of uranium with sulfuric acid. The optimum sulfuric acid concentration was found to be 0.03 mole 11 -'for a 25% pulp density suspension. The order of reaction with respect to sulfuric acid concentration was found to be ns0.75. The best results vith hydrogen peroxide were obtained at a 4.64 molar ratio of 6202 to U in the ore. The order of reaction was found to be zero with respect to hydrogen peroxide concentration. The theoretical maximum rate effect of Hz02 on uranium extraction was derived as Vm = 8.15 x mole &-'min-'. The highest rate experimentally attained was 8.09 x mole kL'min-'. It was found that the uranium extrac- tion was not affected by the pulp density up to the 50% used in this study. However, the final yieldswere significantly higher (over 90%) for leaches carried out in the presence of Hz02 than (less than 90%) for leaches carried out in the absence of H202. The reaction was found to follow a first order course with respect to substrate concentration (pulp density) regardless of the presence of H202. The effect of temperature was more explicit at moderate tempetatures (30 to 55 C) than at lower (10 C) or at higher (70 C) temperatures. At this latter temperature an almost complete extraction was realized even without H202. The apparent activation energies were found to be AEa = 2.68 kJ mole-' in the absence of H202, 0.5 kJ mole-'with Hz02 at 40 C to 70 C. and 4.72 kJ mole-' with Hz02 at 10 C to 40 C. All these activation energy values suggested that the uranium extraction process is diffusion controlled regardless of the presence of H202. Further, the change in activation energy in the presence of Hz02 indicates the possibility of change in the reaction mechanisms at lower and higher temperatures.

Jan 1, 1980

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By G. W. P. Rengstorff

In an effort to find an oxidation-resistant alloy of molybdenum, binary and ternary alloys containing aluminum, chromium, cobalt, iron, nickel, silicon, titanium, tungsten, vanadium, and zirconium were screened. Fourteen other alloying additions were also tested. Many of the alloys were more oxidation-resistant than molybdenum, but none were entirely satisfactory. MOLYBDENUM oxidizes extremely rapidly above 1450°F in air. At 1800°F, a loss of metal at the rate of 0.1 in. in 4 hr is typical. The high speed of this oxidation may be judged by comparison with the oxidation rate of 0.1 in. per year (0.00005 in. in 4 hr), sometimes taken as the maximum permissible oxidation rate at 1800°F for a satisfactory Fe-Cr-Ni alloy. Great strides have been made in the development of coatings and cladding to protect molybdenum from oxidizing atmospheres. These developments in surface protection will undoubtedly make it possible to take advantage of the excellent hot strength of molybdellum and its alloys in many new applications. Still, even the best coating can protect molybdenum only as long as the surface layer is unbroken. Research was undertaken to determine whether an alloy of molybdenum could be found which would resist oxidation. Such an alloy would not deteriorate suddenly when the protective surface layer was destroyed in a small area. In seeking an alloy of molybdenum to resist oxidation, the physical properties of molybdenum could not be sacrificed entirely. The development of an alloy with the desired resistance to oxidation was not achieved. The information obtained on the effect of a large number of elements on the oxidation of molybdenum is, however, of value in the development of coatings. Indeed, many of the alloys tested for oxidation resistance were already known to have poor mechanical properties but were tested to aid in the development of coatings. Oxidation of Molybdenum The rapid oxidation of molybdenum is usually attributed to the volatility of Moo,,. Gulbransen and Wysong have shown that molybdenum oxidizes very slowly up to 850°F, the temperature at which the oxide film begins to evaporate. Melting as well as evaporation of molybdenum oxides promotes the oxidation of molybdenum. MoO melts at 1465°F. MOO, the oxide which is believed to form at the metal-oxide interface, combines with MoO, to form a eutectic having a melting point of 1432°F.' The liquid oxide, even if nonvolatile, could cause poor resistance to oxidation by allowing easy transport of molybdenum and oxygen ions through the oxide. Actually, a sudden increase in the rate of oxidation of molybdenum at 1460°F has been observed to coincide with the appearance of a liquid phase. The formation of a volatile oxide is not unique with molybdenum. The problem is also encountered with vanadium, tungsten, and some of the Pt-Pd group of metals. Vanadium not only forms the volatile V2O3 but, like molybdenum, forms a liquid oxide coating. Few attempts have been made, however, to prevent the rapid oxidation of these metals by alloying. Oxidation of Molybdenum Alloys At the beginning of this work, very little was known of the oxidation resistance of molybdenum alloys. It was known that molybdenum disilicide (with 37 pct Si) has extremely good oxidation resistance,' but this compound is so brittle that it has few uses. It is an effective protective coating for molybdenum when allowance can be made for its brittleness. Chromium was known to retard the oxidation of molybdenum,' but at least 50 pct Cr was necessary to have an appreciable effect. Other, unpublished, reports show that a few other alloys have been given preliminary tests, but the results have not been promising." Choice of Alloys to be Investigated An alloying element might be expected to protect molybdenum in either of two ways: Its oxide might combine with molybdenum oxide to form a stable, nonvolatile complex oxide (a molybdate); or the oxide of the alloying element might form in preference to molybdenum oxide, developing an impervious layer which would prevent the formation of a volatile molybdenum oxide. The knowledge available about the formation of molybdates was meager. Therefore, the initial study was made on alloys of molybdenum with elements having especially stable oxides. On this basis, binary and ternary alloys containing the following six elements were investigated: aluminum, chromium, titanium, zirconium, silicon, and vanadium. Nickel was also added as an alloying element. Although it does not form a more stable oxide than molybdenum, it does impart some oxidation resistance to copper and iron. Its inclusion in the study was fortunate because its alloys proved to be the most promising of those first tested. Apparently nickel formed a stable molybdate. Because nickel was effective in reducing the oxidation rate of molybdenum, the elements iron, cobalt, and tungsten were added to the list. The ten alloying elements mentioned form ten binary and 45 ternary alloying systems with molybdenum. A series of alloys was tested in each of these systems. In addition, at least one test was made on the effect of each of the following alloying elements:

Jan 1, 1957

By R. W. Shoenberger, J. D. Clendenin, W. L. McMorris, N. Schapiro, B. R. Kuchta, A. A. Terchick, R. J. Gray, J. G. Price

INTRODUCTION * The United States is fortunate in having enormous reserves of metallurgical-grade coals. Although these coals are better in quality and more accessible than most coals found throughout the rest of the world, the best grades of these coals are being depleted. Consequently, more efficient exploration tools and techniques, such as advanced methods of core drilling and logging, correlation by palynology,** stratigraphy, paleontology and petrography are being used to help assess the extent and quality of the remaining coal reserves. Exploration and assessment of new and existing coal properties become of utmost importance in determining (1) the economic justification for mining the coal, (2) the optimum design of the preparation plant and (3) the most effective use of the coal. Fortunately, the cost of mining coal has remained stable because of better mine planning, more efficient operations and increased mechanization of mining operations. However, increased mechanization raises the amount of impurities in the coal mined, and this requires more and better coal beneficiation to meet the more stringent quality requirements set by the market. Besides, mechanical miners also produce relatively fine coal and, to ensure maximum liberation of impurities, much of the coal presently being used must be crushed to a finer size prior to preparation. The bulk of all coals presently used in this country is mechanically cleaned, much of it at a lower specific gravity than in the past. This necessitates the use of new and improved processes and equipment for coal washing and recovery, such as heavy-medium cyclones and vessels, and froth flotation cells. However, because wet-cleaning processes are pre- dominant in the United States and fine coal retains large amounts of moisture, the increased production of cleaned fine coal accentuates the need for new or improved methods and equipment for dewatering and drying this coal. The larger amounts of coal being beneficiated and the use of new and improved beneficiation processes will aid in controlling and ultimately eliminating sources of pollution. Modem coal markets demand coals that meet rigid specifications. Most coals are purchased under contracts that specify moisture, ash, and sulfur contents, or heating value, depending upon the end use. There has also been a growing trend toward specifying other properties, including particle size and coking capability. These specifications may include not only the * Editor's note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections prepared by each individual as has been done in other chapters. ** Palynology is the study of plant microfossils, especially spores, pollen, and other types of fossils not usually studied by paleontologists.

Jan 1, 1968

The Institute offers two distinct relationships to. students: one is an individual relationship as a Student Associate; and the other is a relationship with local organizations of students, known as Student Chapters of the AIME This individual relationship is set forth in Section 8 of Article I of the AIME Bylaws, as follows "A student in good standing in an approved school, who has been nominated by at least three instructors of the nominee (one of whom must be an Institute member), may affiliate with the Institute as a Student Associate by payment of $4.50 annual fee, for which he shall receive one monthly journal and be privileged to attend meetings of the Institute and to use the Engineering Societies Library and the Personnel Service A student may remain such until December 31 of the year in which he ceases to be in university residence as a student "

Jan 1, 1952

By Geoffrey Purcell

Although the extractive metallurgist has not yet tackled the problem of getting blood out of a stone, he must, when faced with the mini- metal values of today's ores, believe that this ultimate miracle will soon be expected of him. Even assuming that some plausible professor at one of the few remaining minerals industry schools could persuade the National Science Foundation to sponsor such a sanguine research project, the funds might have to go begging for want of a graduate metallurgist. Falling enrollment in fields devoted to nonrenewable mineral resources, long a matter of grave concern to educators, is now recognized as a problem of great national consequence urgently needing a solution. While the law of supply and demand might eventually be expected to right the imbalance of engineers, time is not on our side and action to correct the shortage is required now.

Jan 1, 1970

By John McCaslin

ONE of the most common technical terms in the U. S. today is automation-a word not listed in the 1946 dictionary. The influence of automation on the national economy has been tremendous. It has even been the subject of congressional investigations. Automation, writes Aronson, substitutes mechanical, hydraulic, pneumatic, electric, and electronic devices for human effort and decision? Automatic devices and instruments are used extensively in some industries, but many others have yet to take full advantage of these great discoveries. The petroleum industry has been a leader in using automatic controls-some refineries are almost completely controlled by automatic devices. The field of geophysics is entirely dependent on instruments and has progressed at almost exactly the same rate as improvements in instrumentation. In metallurgy and mineral dressing use of instrumentation is increasing very rapidly. Mining engineers throughout the country are beginning to think in terms of instruments and controls.

Jan 3, 1958

By F. J. Plecity, J. T. Michalak, W. C. Leslie

Isothermal recrystallization and grain growth in zone- and vacuum-melted irons and Fe-Mn alloys, up to 0.60 pct Mn, were studied in the range 480° to 650° C, after 60 pct cold reduction. In initial stages, rate of grain growth and rate of recrystallization of iron decrease with time. The recrystallization is typical of a growth-controlled process, and rate of growth is determined by the extent of recovery. Mn decreases rates of growth and of recrystallizatzon. The recrystallization process changes at about 0.30 pct Mn and nucleation may become time-depetzdet~t. In recent years, considerable effort has been expended in determining the effects of solute elements on recrystallization and boundary migration in fcc metals. The results have indicated that the effects produced by single solute additions are dependent upon both the element added and its concentration.'-' In contrast, there have been very few attempts to determine the characteristics of recrystallization and boundary migration in high-purity bcc metals, especially after heavy deformation, and the effects thereon of single solute elements.9-11 This study was undertaken to determine the recrystallization characteristics of various "high-purity" irons and the effects of manganese additions at two levels of base purity. It was hoped that the information obtained would improve our understanding of the recrystallization of pure metals and aid in formulating a theory for the effect of solute elements. The interest was not entirely academic, for the annealing of low-carbon steels, which is of very great commercial importance, is but poorly understood. MATERIALS The compositions of the irons and iron-manganese alloys used are listed in Table I. The zone-melted iron and Fe-Mn alloys were made by Battelle Memorial Institute. Iron S-1 was arc-melted in a water-cooled steel mold in an argon atmosphere. The ingot was forged into a bar, then given two horizontal zone-refining passes in an alumina boat. Iron V-4 was treated in a similar manner, but was not zone-refined. The iron for the zone-melted Fe-Mn alloys was induction melted in vacuum in MgO crucibles and cast into alumina molds. The ingots were forged into bars, machined to shape, and a groove milled down one side of each. The best available electrolytic Mn was placed in the grooves, and the bars were zone melted. The vacuum-melted Fe-Mn alloys were induction melted in this Laboratory in MgO crucibles and poured into cast-iron molds. Iron V-5 was purchased from National Research Corp. in the form of a small vacuum-cast ingot. The low-carbon steel was made by induction melting in air at the U.S. Steel Corp. Applied Research Laboratory. The history of the materials prior to the final cold reduction differed; these details are given in the Appendix. The penultimate grain size of the principal materials was kept in the range ASTM 2 to 4, except for the low-carbon steel. PROCEDURES The cold work prior to the final recrystallization anneal was kept constant at 60 pct. It is known that rolling procedure can influence the kinetics of recrystallization of ironI2; therefore, all specimens were rolled in one direction only, between clean,

Jan 1, 1962

By D. L. Kelley

High-viscosity water injection has been proposed for use in reservoirs containing high-viscosity crude oils. Previous publications have largely ignored the possible effects of the connate water on the proposed process. This paper describes experimental work which indicates that the connate water will be forced ahead of the injected water to form a bank of low-viscosity water. This decreases the oil recovery which would be expected if such a bank were not formed. These effects are shown for a range of fluid mobilities and connate-water saturations for a five-spot injection system. In general, oil recoveries using viscous water are significantly greater than for untreated water even though they are less than would be expected if no connate water bank were formed. INTRODUCTION The effect of mobility ratio on the oil recovery of wa-terfloods has been known for many years. Muskat first pointed out that the fluid mobilities (k/µ) in the oil and water regions would affect the performance of the water-flood, and he estimated the general effect of these variables.' Since this early work, studies of the effect of mobility ratio on secondary recovery have been reported where mathematical,' potentiometric3 and scaled flow models' were used. These studies have shown that a reduction in the mobility ratio between the oil and the displacing fluid would cause additional oil recovery when water-flooding reservoirs containing viscous crude oils. Studies reported by Pye- nd Sandiford 8 have indicated that chemicals to increase injection water viscosity are now available and can be used to reduce the over-all mobility ratio of a waterflood. Where mobility ratios are controlled by the injection of viscous fluids, the connate water of the reservoir can play an important part in the displacement of the reservoir oil. The purpose of this study was to determine the effect of the connate-water saturation in waterfloods where viscous waters are used for injection. DISPLACEMENT OF THE CONNATE WATER Russell, Morgan and Muskat7 were the first to recognize the mobility of connate waters in waterflooding. They conducted waterfloods on oil-saturated cores containing 20 and 35 per cent irreducible water saturations, and found that from 80 to 90 per cent of the "irreducible" water was produced after only one pore volume of water was injected. However, their experiments were conducted at rates of flow significantly higher than those ordinarily occurring in waterfloods. Also, the cores were only from 4.0 to 8.5 cm long. Brown 4 studied a 100-cm linear sand pack which had been prepared to contain connate water and oil. He used 140- and 1.8-cp oils with injection water of essentially the same viscosity as the connate water. He found that all of the connate water was displaced by the injection water in both cases. However, the injection volumes required for complete displacement of the connate water were considerably higher in the case of the more viscous oil. To verify the results of the foregoing experiment, a 10-ft-long linear model was constructed by packing 250-300 mesh sand in a 1/2-in. diameter nylon tube. The model was evacuated, saturated with a brine of 1-cp viscosity, and flooded with a 41-cp mineral oil to the irreducible water saturation of 10.9 per cent. The model was then waterflooded by the injection of a water solution which had an apparent viscosity of 42.6 cp. The solution consisted of 0.5 per cent methylcellulose in distilled water. The viscosities of the oil and connate water were measured with an Ostwald viscosimeter. The viscosity of the polymer solution was calculated by Darcy's law using pressures measured during actual flow conditions. The ratio of the mobility in the oil region to the mobility in the inject ion-water region was approximately 0.32. The mobility ratio of the oil region to the connate-water bank was approximately 14. The mobility ratio between the connate-water bank and the injection water region was 0.024. Approximately 84.5 per cent of the recoverable oil was produced before water breakthrough. Immediately following breakthrough, oil and connate water were produced at an increasing water-oil ratio until the viscous injection water broke through. At viscous-water breakthrough, 96 per cent of the original connate water had been produced. After breakthrough of the viscous water, there was no additional production of connate water or oil. The near-

Jan 1, 1967

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall's work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann's approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen's approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By M. O. Holowaty, C. M. Squarcy

Blast furnaces are the tools of men, and it is men who have made them great. Here is presented the story of the Ironmakers-the men who first poured hot metal into what would someday be the sinews of a nation. W HEN the Jacobean merchant adventurers bade farewell to the first ship of colonists sailing for the new land, they instructed them to direct all their skill and energy to grow silk worms in Virginia. The adventurers felt sure that they could flood the market with highly priced and much desired goods like silk, sugar, tea, and indigo. They were also convinced that they would fill the needs of the mother country for iron. Early iron production in the colonies The merchants certainly had a wonderful imagination, for silk and indigo were just as exotic in Virginia as they were in England. The settlers found it more profitable to raise tobacco on the vast stretches of the free, fertile land. Thus the plans of settlers clashed with those of The Virginia Co.; and only point of agreement was the desire to produce iron. But, even there the motives of the settlers and those of The Virginia Co. of London were worlds apart. The settlers wanted to produce the tools badly needed in the colony, while the Company desired to cash in on the rising demand for iron which the home industry could not satisfy. Both the settlers and the Company lost no time trying to find iron ore. Locations of the early mines are not known. If, however, the reports of the Irishman, Francis Maguel, can be trusted, as early as 1609 a ship sailed for England with a load of 17 tons of crude iron which the East India Co. purchased at £ 4 per ton. The iron was of excellent quality and considered the best iron made of non-English ore that was ever purchased.

Jan 1, 1961

Coal was known in this county before 1819, but there is no record of its use before that year. In that year a furnace, the first one built in the northwestern countries, was put in blast on Bear Creek; it was built to use coke and its first blast was with this fuel, which was made in heaps, but the blast was too weak and the furnace chilled after two or three tons of iron had been made. Charcoal was then substituted, and this use of coal ceased.1 In November of the same year a resolution was adopted urging state aid for a road from Kittanning to. Hamilton, New York: "that this road will increase the trade and industry of the whole county, between Pittsburgh and the New York line; and that our soil will in consequence be better tilled, our mines of coal, of iron and of salt, be better wrought, etc."2 In 1828 an advertisement of lands situated near Freeport on the Allegheny River and contiguous to the canal nearly completed between the Kiskiminitas and Pittsburgh stated that they contained "large and never failing springs, Coal in abundance, and a great deal of Fine Timber."3 In 1830 there were said to have been 24 salt wells in this county producing 327,000 bushels of salt, chiefly on the Kiski and Allegheny Rivers. In 1837 there were a number of wells in the vicinity of Freeport. As all the salt works on the Conemaugh River, were using coal long before 1830,4 it is safe to say that a considerable tonnage of coal was used for some years in these plants. In 1837 a tract of land in Clarion Township having a new saw mill and abounding "in Stone Coal" was offered for sale,5 and also one in Toby Township having "an abundance of the best quality of iron ore and stone coal."' In 1839 an advertisement in the Pittsburgh Mercury said

Jan 1, 1942

By J. F. Myers, F. M. Lewis

THE selection of the proper type of flotation machine involves the consideration of a wide variety of factors. Under any condition, all types of machines will promote some kind of separation. Obviously, the correct way of deciding which type of machine is best suited for a particular problem would be to set up all types of machines and test them out in a competitive manner, but the vast number of small concentrating plants are unable to make such complete and exhaustive tests. The experience of the authors of this paper indicates that if all the factors involved in any particular problem can be determined, and if all the flotation-machine characteristics are understood, some basis for selection could be arrived at other than actual comparison. This paper is presented to show how the process factors and machine characteristics have been combined at the mills of the Tennessee Copper Co. from studies of several types of flotation machines. At the two mills of the Tennessee Copper Co. in the Ducktown Basin of Tennessee, four distinct flotation separations are made on the complex sulphide ore. Three different concentrates are produced from the ore-in the order of their importance: iron concentrate, copper concentrate, and zinc concentrate. Four different types of flotation machines are used. The selection of these four machines, for the plant operation, was based upon the study and operating experience of the machine units shown in the following list: Fagergren machine; square cell, size 56 inches Fagergren machine; level type, size 56 inches Denver machine; conical disk impeller, size 24 inches Denver machine; receded disk impeller, size 24 inches Minerals Separation Sub-A, size 24 inches Munro-Pearce deep cell, pneumatic Southwestern air machine, Hunt principle To date the study of flotation machines has been confined almost entirely to the rougher circuits. The various cleaning operations, being relatively a much simpler matter, have not been investigated so thoroughly. Table 1 shows a typical analysis of the two ores as well as of the mineral content. []

Jan 1, 1944

By R. S. Hutton

WHEN I had the honor of receiving an invitation to give the-Institute of Metals Lecture, it occurred to me that it might be of interest to review the advances which have been made in refractories, considering how important these materials of construction are in the carrying out of many metallurgical operations and what a large factor they represent in our costs of production. Frankly, I can claim no recent contact with the refractories industry and what little work I myself have been concerned with has been rather unorthodox in character. However, perhaps in consequence of this, I can approach the review without bias and include some suggestions which may prove stimulating or provocative to some of you, who have a more intimate knowledge of refractories and their uses than I Possess. It is neither possible nor necessary for me to survey the progress of industrial refractories, for this has been so thoroughly undertaken by others1-7 in recent publications. Perhaps the best way to get a broad picture of this progress is to compare the Faraday Society Symposium on Refractory Materials 20 years ago8, containing a report on one of the first attempts at standardized testing, with the American Society for Testing Materials Committee Report of February 1935. Suffice it to say, lest my provocative remarks be misunderstood, that I do appreciate that great advances have been made, particularly by companies that have established their own research laboratories and by universities and cooperative research institutes working for the common weal of groups of manufacturers or for national and international progress. The scientific study of the constitution diagrams of binary and ternary refractory oxides, which American workers have been foremost in under-taking, ? led by the work of the Geophysical Laboratory at Washington, has laid a firm foundation for the whole subject. It should be remem-bered, however, that to a much greater degree than with the constitution of metal alloys, the equilibrium conditions are so sluggishly arrived at

Jan 1, 1937

By E. W. Krampert

Oil development continued active in Wyoming during 1937, with much of the interest centered on prospecting for new pools, following a rather intensive seismograph play in 1936. The new fields of Lance Creek, Medicine Bow and Quealy were the centers of intense development in proved areas, but routine drilling occurred in most old fields. A new and deeper producing horizon (the Leo sand) was opened up in the Lance Creek field, which materially extends the producing area and will probably account for continued active development during 1938. The discovery in 1936 of oil in the Eocene Wasatch formation at Powder Wash, northwestern Colorado, tended for a time to stimulate prospecting in the deep Tertiary basins, but this interest as rapidly declined after drilling several failures on similar structures and the discovery that the productive area at Powder Wash itself was very small. A most interesting test of an Eocene structure was drilled by The Superior Oil Company of California on the South Baggs structure, in Carbon County, Wyoming. South Baggs is one of the best developed structures in the Red Desert Washakie Basin, which also includes the Hiawatha gas field and the Powder Wash gas and oil field. The Superior Oil Co. started the well according to contract but apparently had lost interest in the prospects, for it abandoned the well at 2138 ft. without testing the oil-bearing and gas-bearing horizons of the Wasatch. The Sinclair Wyoming Oil Co. drilled a deep test in the Muskrat gas field to the Madison. This well discovered oil in the Embar formation, which was considered noncommercial because of depth. After the Embar was abandoned the hole was plugged back and the various sands tested by shooting through the casing with the Lane-Wells gun. The Lakota sand was found to contain high-pressure gas and the well was completed as a 24-million-foot gasser at 2175 lb. rock pressure. This is a new sand in an old field. The Italo Petroleum Co. drilled a flank well on the Hamilton dome structure and found oil in the lower Embar formation. Thk merely extends the limits of production, as one old well on the structure had

Jan 1, 1938

Undoubtedly other members have given their lives in the Service of the United States and the Allies during the past four years, but the following biographical notices are all that have reached us as yet. Lewis Newton Bailey Lewis Newton Bailey died of pneumonia at Camp Merritt, N. J., Apr. 30, 1918, at the age of 34 years. He was Master Engineer, Senior Grade, in the Fourth Regiment, U. S. Engineers, and although he was offered a commission as First Lieutenant shortly after enlisting, he preferred not to accept it until he had reached France. By those who knew him well, this lack of eagerness for promotion will be recognized as consistent with his whole character. Mr. Bailey was born at San Diego, Cal., May 28,1884, and graduated from the University of California, College of Mines, in 1906. He joined the American Institute of Mining Engineers in 1916. During 1904 he was employed at the cyanide plant of the Buckeye mines, Forest Hills, Cal. In the autumn of 1909 he went to the Coeur d'Alene District, Idaho, and was first employed on construction work of the Bunker Hill & Sullivan Mining & Concentrating Co'., with a short intermission at the Hercules mill, after which. he was sampler and assayer for the Bunker Hill & Sullivan Co. until May, 1910, when he was obliged to return to California to attend to family interests. Returning to the Coeur d'Alene district in November, 1911, he was given charge of remodelling and operating the mill of the Coeur d'Alene Development Co., treating the output of the Ontario mine; this work he performed with credit and complete success. In December, 1914, he returned to the Bunker Hill & Sullivan Co., as assistant metallurgist and mill superintendent, his work consisting mainly in the testing and improvement of concentrator practice, which he continued with great credit until August, 1915, when family considerations required that he again return to the home of his parents at San Diego. Mr. Bailey was characterized by energy, both physical and mental, by devotion to his friends, associates and employer. He was particularly successful in his relations with the men under him and, in fact, was thoroughly well likcd by everybody with whom he came in contact.

Jan 1, 1920

By Rossiter Raymond

JOHN BIRKINBINE was born Nov. 16, 1844, at Reading, Pa., the eldest son of H. P. M. Birkinbine, widely known as a hydraulic engineer. The family removed subsequently to Philadelphia, where, as a young man he established with his father the office now continued by his sons, after more than 60 years. His education was received at public schools, the Friends' High School in Philadelphia, the Hill School at Pottstown, Pa., and the Polytechnic College of Pennsylvania, where his studies were interrupted in 1863-4 by service in the Union Army, which included participation in the battles at and around Gettysburg. Later, he devoted two years to work in a machine shop; and subsequently he became associated with the late P. L. Weimer, under the firm. name of Weimer & Birkinbine, operating the Weimer Machine Works at Lebanon, Pa. Much of his work was in mining, metallurgy, and blast-furnace construction. As manager for the South Mountain Mining & Iron Co. he carried on experiments with various fuels for iron-ore smelting while maintaining the furnace in constant operation. The carefully recorded results obtained were widely published, and are referred to in text-books by other metallurgists as most complete. From his Philadelphia office he was sent to nearly every State, and to Canada and Mexico, for examinations, reports, constructions or improvements in iron-ore mines, blast furnaces, iron works, water supplies, hydraulic development, irrigation projects, etc., and his engineering knowledge was requisitioned by several European corporations. A number of business trips were made to Mexico, beginning with a visit to the Cerro de Mercado at Durango, before railroads were established in that portion of Mexico, to make a critical examination and report on this "Iron Mountain." Later visits covered other localities and engineering problems, familiarizing him with the major part of the iron industry in Mexico. The late disturbed political conditions in that Republic have retarded the probable enlargement, modernization, and improvement of much of the iron and steel industry of Mexico, upon which he investigated and reported for various capitalists on both continents. One interesting subject included in these reports was a proposed electric furnace, to be operated by energy from water power.

Jan 7, 1915

By Rossier W. Raymond

John Birkinbine was born Nov. 16, 1844, at Reading, Pa., the eldest son of H. P. M. Birkinbine, widely known as a hydraulic engineer. The family removed subsequently to Philadelphia, where, as a young man he established with his father the office now, continued by his sons, after more than 60 years. His education was received at public schools, the Friends' High School in Philadelphia, the Hill School at Pottstown, Pa., and the Polytechnic College of Pennsylvania, where his studies were interrupted in 1863-4 by service in the Union Army, which included participation in the battles at and around Gettysburg. Later, he devoted two years to work in a machine shop; and subsequently he became associated with the late P. L. Weimer, under the firm name of Weimer & Birkinbine, operating the Weimer Machine Works at Lebanon, Pa. Much of his work was in mining, metallurgy, and blast-furnace construction. As manager for the South Mountain Mining & Iron Co. he carried on experiments with various fuels for iron-ore smelting while maintaining the furnace in constant operation. The carefully recorded results obtained were widely published, and are referred to in text-books by other metallurgists as most complete. From his Philidelphia office he was sent to nearly every State, and to Canada and Mexico, for examinations, reports, constructions or im-provements in iron-ore mines, blast furnaces, iron works, water supplies, hydraulic development, irrigation projects, etc., and his engineering knowledge was requisitioned by several Eukopean corporations. A number of business trips were made to Mexico, beginning with a visit to the Cerro de Mercado at Durango,,before railroads were established in that. portion of Mexico, to make a critical examination and report on this "Iron Mountain." Later visits covered other localities and engineering problems, familiarizing him with the major part of the iron industry in Mexico. The late disturbed political conditions in that Republic have retarded the probable enlargement, modernization, and improvement of much of the iron and steel industry of Mexico, upon which he investigated and . reported for various capitalists on both continents. One interesting subject included in these reports was a proposed electric furnace, to be operated by energy from water power.

Jan 1, 1916