Search Documents

By Claiborne C. Van Zandt

THE heavy postwar demand for Portland Cement has created shortages that are gradually being overcome by increases in plant capacity. In the post-war period, the Lone Star Cement Corp. has expanded several of its existing 15 plants and has built 2 new plants, now in operation, with a third new plant under construction in Brazil, of design somewhat different from that of the two preceding ones. The new domestic plants are located at Lone Star, Va., near Roanoke, and at Maryneal, Tex., near Sweetwater, and went into operation during 1951. Each plant is equipped with two rotary kilns and has an initial capacity of 1,500,000 bbl per year, or 6,000,000 sacks. The total cost of each plant was about $10,500,000, and on this basis $7.00 in 1951 money are required per bbl of annual capacity; at 376 lb per bbl, this corresponds to $37.00 per ton of output. The investment corresponds to approximately $80,000 per hourly-wage earner employed. The purpose of this paper is to describe the most interesting design features of the two new and almost identical Lone Star plants. Why the Dry Process Was Chosen The two new domestic Lone Star mills employ the dry process because: 1-The raw materials at both properties are particularly suitable and can be dried very, readily. 2-The Maryneal, Tex., plant does not have water available for slurry. 3-Very substantial kiln fuel savings can be obtained. 4-Dry raw grinding reduces ball and liner wear and- general maintenance, without any sacrifice in power. Operating costs to date have more than justified the choice of the dry process for these two plants. Raw Materials The chemical composition of Portland Cement raw material after crushing, grinding, and mixing, but before burning, is about as follows: [ ] sometimes tailings from an iron ore concentrating plant. Certain objectionable materials occur in raw mix: magnesia, limited in cement to 5 pct, in excessive amounts; alkalies, as sodium and potassium; phosphorous; and sulphur, generally present in coal and oil. The Roanoke raw, materials are dense limestone and shale. The Maryneal materials are soft limestone and a hard brittle clay that can be handled much like shale. Sand and iron ore are required in small quantities. General Plant Layout and Construction The two plants are so similar that one joint description will cover both, with such exceptions as will be especially indicated. The crushing plant is located in the quarry, and raw material is conveyed by belt to the storage building, where all materials are stored and handled. Fig. 1 identifies the various structures of the Roanoke plant. The large storage building is used for the storing and handling of all materials, including limestone, shale, sand, iron ore, coal, clinker, and gypsum. Directly adjoining the storage building is a structure under a similar arched roof, containing the raw and clinker grinding departments and the electrical substation. The discharge ends of kilns and coolers, and coal or gas burning equipment are also placed at one end of the mill building. The 340ft long kilns extend away from the main buildings to form the long leg of an L, at the end of which is the feeding and kiln dust collecting equipment, and the raw blending silos are conveniently located adjacent to the feed end of the kilns. The machine shop, storeroom, electrical shop, foremen's office, service rooms, and meeting hall are combined in one structure in the center of the plant, and the office and laboratory are close by. The cement silos and packhouse do not have to be tied directly into the manufacturing process and are therefore located at a point convenient to the railroad tracks.

Jan 1, 1952

By G. E. McElroy

Though air jets occupy only a minor role in the ventilation of mines and other enclosures, their importance in this respect is greater than is commonly recognized and may be considerably increased as our conception of their modes of operation becomes clearer. The object of this paper is to discuss some of the ways in which air jets are involved in mine ventilation and some possible applications to the ventilation of mines and other enclosed spaces. The mention of air jets ordinarily suggests the use of some form of an air injector, such as the Venturi blower occasionally used for auxiliary ventilation in mines, or the Saccardo (injector) system used to a limited extent for ventilating railroad tunnels. Actually, the term covers such common phenomena as the discharge of air from fan pipes and coal-mine line brattices, and even from smoke stacks and fans. A knowledge of the general mode of air entrainment by jets also helps to explain certain phenomena—some mine-gas explosions, for instance—that otherwise would remain obscure. Jet action has been involved in three recent series of Bureau of Mines experi-ments in which the author has participated: experiments on fan-pipe discharge, On the dilution of gases discharged from a stack and On the ventilation of a ship's hold. Available data on the discharge of jets into large openings and on the design and performance of air injectors have been analyzed in considerable detail and supplementary experiments are planned for after the war. The results of the fan-pipe experiments have been combined with the analyses of data on jet discharge into large spaces, and have been published.' The results of the stack-gas dilution tests, which refer to a jet discharged into a crosswind, have also been published2 and a paper on the design and performance of injectors has been prepared for publication.3 These technical experiments and analyses form the background and the documented evidence for the following nontechnical discussion of the use of air jets in mine ventilation. Jet Characteristics The jets commonly encountered are those in which the air is in turbulent— as opposed to laminar, or streamline-— motion. The characteristics under discussion apply only to such turbulent jets and have their basis in theories of the mixing of turbulent air currents. Such jets have basic characteristics that are present, though variable in form, regardless of whether the jet expands freely in space, whether the expansion is limited by adjacent walls, or whether the jet propels air through a flow circuit. They expand at definite angles and entrain the surrounding air, even though the entrained air must be obtained by recirculation of their own air streams. As the quantity of air in motion in the mixed stream increases, the average velocity of the stream decreases.

Jan 1, 1946

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

In an earlier study at this laboratory,' the authors investigated the solid solubility of holmium in copper, silver, and gold, and also the melting point of the first eutectic on the noble-metal-rich side in these systems. In a more recent study of the solubility of rare-earth metals in gold at this laboratory. Rider, Gschneidner, and McMasters2 noted that the reported eutectic temperature in the Ho-Au system was lower than the corresponding eutectics in systems of dysprosium and erbium with gold. A redetermination of the eutectic temperature in the Ho-Au system with the same alloy used in the original study showed the eutectic temperature to be 810°C instead of 778°C as originally reported. (The eutectic temperatures in the Ho-Ag and Ho-Cu systems were also redetermined and were found to be 795" and 864°C compared to 787° and 868°C, respectively, which were reported originally.) Since this large change in eutectic temperature made the solubility data appear questionable, new alloys were prepared, heat-treated, and examined metallographically. The procedure of sample preparation and heat treatment used in the original work' was followed except longer heat treatments were used ranging from 7 days at 600°C to 6 hr at 900°C. The results obtained are shown in Fig. 1. There is good agreement between the two studies in the maximum solubility of holmium in gold. Since the slope of the solvus is less pronounced in the present study, the extrapolation to 550°C shows a solubility of 1.6 wt pct Ho in gold compared with 1.0 wt pct in the original work. Since additional data were obtained and longer heat treatments were used in the present study, the larger value is believed to be more accurate. The authors wish to express their appreciation to P. Rider and K. A. Gschneidner. Jr., for bringing this discrepancy to their attention, and also to D. Thompson for assisting in the present study.

Jan 1, 1965

By N. A. Warner

Dense cylindrical specimens of artificial hematite were reduced in hydrogen over a range 0-f total pressures between 0.1 and 1.0 atm and temperatures between 650" and 950°C. Hydrogen reduction at a total pressure of 1.0 atm in the presence of a chemically inert diluent and reduction in hydrogen/water mixtures were also studied Znter.face movement during reduction was followed using metallographic techniques. Substantiu1 partial-pressure gradients are shown to exist in both the gas film and the reduced iron layer. The results are consistent with a mixed-control mechanism involving an interaction of gaseous-difusion effects with a first-order reversible chemical reaction at the iron/wüstite interface. Over the hydrogen-pressure range of 0.1 to 1.0 atm, the rate is not directly proportional to the hydrogen pressure in the bulk gas stream. Nitrogen dilution of the reducing gas masks the true effect of hydrogen partial pressure by influencing the effective molecular dif-fusivity and gives an apparent first-order relationship. The transport of hydrogen and water vapor across the iron layer is consistent with molecular gaseous diffusion rather than a Knudsen diffusion mechanism. ALTHOUGH the literature on the reduction of iron oxides is very extensive, it is only comparatively recently that a definite quantitative model for the reduction of hematite has been proposed. This development has been largely due to the work of McKewan. An extensive literature review of previous work has recently been compiled by Themelis and Gauvin. Exclusive control by gaseous diffusion in the reduction of hematite has been recently advocated by Kawasaki and coworkers.' Although the results of the latter workers are of considerable practical significance, the extreme porosity (approximately 30 pct) of their specimens precludes their application to a kinetic evaluation of the reduction of dense polycrystalline hematite. The salient features of the kinetic model used by McKewan for the gaseous reduction of dense hematite at temperatures in excess of 560°C (when FeO is stable) are: 1) The reduction is a topochemical reaction taking place through 'the series FeO/FesO4/FeO/ Fe; 2) The gas-solid type of reaction takes place only at the FeO/Fe interface and the internal reduction: FeO proceeds by solid state diffusion; 3) The iron layer formed is quite porous and offers negligible impedance to gaseous diffusion; 4) The rate-controlling step in the reduction is a chemical process occurring at the Fe/FeO interface. In view of the relatively fast reaction rates involved when hematite is reduced in a stream of hydrogen, it seemed possible that the simplifying assumptions of negligible diffusional resistance in both the bulk gas phase and the reduced iron layer could introduce serious errors in the interpretation of experimental reduction data. The present work was initiated to elucidate the effect of gaseous diffusion on the reduction rate and to determine its possible influence in the formulation of the reaction mechanism at the metal/oxide interface. EXPERIMENTAL Procedure and Apparatus. Dense cylindrical compacts of artificial hematite were prepared by sintering pressed compacts of reagent-grade ferric oxide, containing 99.6 pct FezO, in air at 1200°C for 80 hr. The resulting compacts had a final porosity of less than 2 pct and a height and diameter of approximately 1 cm. Variations in sintering atmosphere from air to pure oxygen, in sintering time from 20 to 80 hr, and temperature from 1150" to 1250°C had no effect on the subsequent reduction behavior. The reduction of the samples took place in a vertical tube furnace in which was placed a 1-in. transparent silica tube. The 24-in. heated length

Jan 1, 1964

By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar' have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962

By R. A. Hadfield

It seems a specially fitting opportunity to present a paper on the alloys of iron and aluminum at the New York meeting of this Institute, owing to the fact that America has, more than any other country, originated and developed the manufacture of cheap aluminum. The Cowles, Castner, and Hall systems have all originated in the ever-busy brain of our cousin across the water. The problem of cheaply producing this valuable metal has been a difficult one, but to the writer it seems that the more arduous the task the greater the delight with which our American friend attempts to overcome the difficulties surrounding it, and the more vim he throws into the work. Another and equally striking proof of this is to be found in the recent appearance of the already wellknown remarkable work, The Mefallurgy of Steel, by Mr. H. M. Howe, of the Institute of Technology, Boston, Mass. It is to be hopel that this Institute will not be slow to recognize by some special mark its appreciation of this signally valuable and original work. The writer has been led to describe the following experiments, believing that so far no full and exact report has yet been presented to this Institute as to the effect of aluminum alloyed or combined with the metal iron. It has been a special object to make the material as far as possible a true alloy or combination of aluminum and iron, with as small quantities as possible of other disturbing ingredients, such as silicon, manganese, etc. In the material described in these experiments, the total amounts of other elements present (sulphur and phosphorus being disregarded as present in such small quantities) do not exceed about 0.5 per cent. Such material may therefore be probably taken as fairly illustrative of the effect of the metal aluminum upon iron. Since completing the experiments the writer

Jan 1, 1891

By T. M. Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the `active masses' of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. [ ] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, [ ] where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of unfloatable mineral. Hence the first order equation is [ ] It has been proposed by various workers1-3 that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris' has discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1952

By Michael Perch

The fact that coal is a complex organic material and heterogeneous in composition has made its study extremely difficult, particularly in regard to obtaining a fundamental concept of the processes involved in the formation of coke. It has been stated recently that coals are natural polymers and that in a complex reaction such as occurs during carbonization the differences between coals are quantitative and not qualitative. Such being the case, it would be expected, therefore, that a series of coals subjected to exactly the same conditions of coking would produce results that should be related quantitatively to the chemical analyses of the individual coals. In the past, however, this fact was not generally recognized and consequently many empirical test methods were devised for testing coals. The interpretation of the results obtained depended upon comparing a set of data with other data on coals of known characteristics. The testing procedure had to be con- ducted in precisely the same manner each time and not the least requirement in making the interpretation was experience. The test methods varied from those utilizing a gram of coal to the plant-scale tests in which one or more ovens were charged with the test coal. The aim had been principally to find some simple, inexpensive means by which the coke-making and other properties of coal could be predicted. It is not necessary to emphasize the importance of these endeavors, for anyone acquainted with the problems involved in the selection of coals for making coke is well aware of the time and expense involved in making a series of definitive tests.

Jan 1, 1949

By H. H. Rachford, J. Douglas, D. W. Peaceman

A numerical solution of equations describing two-phase flow in porous media shows promise in providing a technique for predicting the displacermet from satlds of oil by water or gas. The description includes the influence of relative permeability, fluid viscosities and densities, graviry, and capillary pressure, and, tholrgh tested ortly for two-dimensional cases, should be eqlmlly applicable in three-dimensional geometry. Two memorical methods ore presented: the first method is quite general in its applicability; the second method can be used only with certain types of boundary conditions but requires less computing. Comparisons of computed results with data from Inhoratory models are presented. These data were taken on a water flood of a strarified model and on water floods of a five-spot model for favorable and unfavorable mobility ratios. On the stratified model, excellent agreement with recovery at breakthrough was obtained; agreement with recovery after breakthrough was poor. In the five-spot model, good agreement was obtainecl with recovery at and after breakthrough. The purpose of this paper is twofold: first, to present a reservoir engineering method requiring knowledge only of rock geometry and the normally measured rock and fluid properties for calculating the multi-dimensional flow of water displacing oil from porous, water-wet rock containing connate water; and, second, to investigate the validity of the method by comparing results of calculations with previously observed displacements in laboratory models. The availability of such a verified technique of reservoir analysis would afford major advantages. First, it would demonstrate that the fundamental macroscopic concepts of two-phase fluid mechanics, i.e., relative permeability and capillary pressure, yield an adequate description of the physical process. Also, since most reservoir rocks appear to be water-wet and contain connate water along with oil, it would provide a method of technical and economic value for calculating the course of oil displacement by water directly from measured reservoir and fluid properties. It is important to emphasize that the calculation is subject only to the limitations of detail and precision of reservoir information, but not to limitations introduced by simplifying assumptions. Further, it would providc almost the only means of examining the influence of factors such as the size and extent of reservoir inhomogeneities and uncertainties in the basic reservoir data. Knowledge of this influence is essential in stating quantitatively the detail required to define a reservoir and in establishing the relation between the uncertainty in the definition of reservoir properties and the reliability of predicted performance. Moreover, in the process of solving a particular problem much detailed information would become available about the displacement process. For example, at each point in the reservoir for all stages of the displace ment. the calculations would yield not only the water and oil saturations but also the direction and magnitude of fluid velocities and the local fluid mobilities. Such dctail is potentially of great value in giving insight into the mechanics of particular displacements. The development of such a method has long been the goal of research in the application of numerical an-alysis to petroleum reservoir enginecrinz. The most complete treatment of the displacement process published to date is that of Douglas. Blair, and Wagner,' which, however, was limited to flow in a single dimension. The method presented in the present work is hascd on the numerical solution of a finite difference analogue of the multi-dimensional differential system describing the displacement process. Although current work has considered only displacement of oil by water from water-wet sands, the differential system for other immiscible displacements, such as gas displacing oil with which it is in phase equilibrium, is quite similar. It should therefore be expected that the technique described will be applicable to displacement by gas as well. The description of the simultaneous flow of fluids through porous media in terms of relative perrncability and capillary pressure has been adequately discussed in the literature and standard textbooks. Sec, for exampje, Muskat. Chapter VII.'

By Frank Firmstone

The furnace from which the brick here referred to were taken, was lined under my supervision and blown-in in May, 1902. It was 75 ft. high and 18 ft. in greatest diameter, and used coke to smelt a lean magnetic iron-ore. The lining was put in as follows:—First, blocks 14 in. long by 6 in. thick; second, 2 in. of loam; third, 13.5 in. of 9-in. fire-brick (one-and-ahalf brick wall) laid in English bond; fourth, red brick to within 2 in. of the iron shell; and fifth, 2 in. of slag-wool between the red brick and the shell. The brand of brick used has been known to me for over 20 years, and in my observation had always proved very durable, notably when used in a small furnace 50 k. high which treated the same magnetic. ore. On revisiting and examining the furnace in March, 1903, it was found that the whole of the lining of 14in. blocks at the top, and for an unknown distance (more than 20 ft.) below, had completely disappeared; and a few weeks later the 13.5-in. lining and the red brick at the top likewise vanished, and the furnace was blown out. N~twithstanding the complete failure of the lining higher up, measurements taken after blowing-out showed no unusual wear in the lower part of the furnace. The exact position in the furnace of the piece of brick-work used in the analysis, given below, is not known; but it came from between 30 and 40 ft. above the bottom. It had formed part of the 13.5-in. wall (no 14-in. brick remaining at that level) and consisted of parts of several bricks so firmly sintered together that fracture occurred indifferently through the joints and through the body of the brick. The joints could, however, be traced by a close examination. The surface which had been in contact with the material in the furnace was covered with a yellowish, translucent glaze, somewhat vesicular, and from

Jan 1, 1904

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts'1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By Jesus P. Manzano

The report of which this paper is a summary was made in 1890 for the Compania Investigadora Mexicana y Americana. Since the region examined covers 900 sq. kilom., chiefly of wooded arid rocky hills, almost without roads, and for the most part uninhabited, While the examination had to be made in two months, of which period more than 15 days were continuously rainy, I need not say that this account is not complete and thorough. I. Geography and Topography. The center of this zone, 19 kilom. SW. of San Luis Potosi, is situated in lat. 21° 24' N., and long. 2° 3' W. of Mexico City. The altitude ranges from 1866 m. (that of San Luis) to . 2816 m. (that of the Realito mountain), in the Sierra de Sail Luis. The topography is hilly—partly wooded, partly bare. The principal more level areas are the Bledos valley on the south, and portions of the haciendas of Tepetates, San Fran cisco and Santiago, on the west. The water-supply is scanty. The two streams that cross the Zone, the Santiago and Bledos rivers, carry water nearly the year through, though much reduced in the dry season. Other streams are torrents of less importance. All the waters of the valley and Sierra of Sail Luis arc absorbed or sink, not passing beyond Soledad de los Ranchos. The Continental di vide is within the Zone, some waters going west to the Pacific, others east to the Gulf of Mexico. II. Geology. Concerning the geology of this district I condense the fol lowing from the memoir, Las Minas de Guanajuato, prepared for the Minister of Fomento by Senor Pedro Lopez Monroy, mining engineer, with which I am entirely in accord. He says, ill substance:

Jan 1, 1902

By A. A. Burr, D. G. Ebeling

The effects of casting texture, grain orientation and grain size upon the performance of Alnico permanent magnets is described. Single-crystal specimens were produced by special sintering and grain coarsening techniques to study the effect of crystal orientation. In addition to texture and orientation effects, an analysis of the results indicates that the permanent magnet performance is impaired by a refinement of the grain size. AN excellent historical review of the development of Alnico permanent magnets has been prepared by Bozorth.1 The desirable permanent magnet characteristics of Fe-Ni-A1 alloys were discovered in 1932 by Mishima.2,3 The work of Ruder' showed that the alloys were age-hardenable, and Betteridge5 defined the best composition and heat treatment for the magnetically isotropic alloy known as "Alnico 3." Horsburgh and Tetley0 increased the energy product by the addition of cobalt and copper, "Alnico 2," and Oliver and Sheddon7 demonstrated that cooling in a magnetic field improved the residual induction of this alloy. Jonas8,9 then disclosed the great practical benefits of heat treating an alloy of higher cobalt content in a magnetic field and the resulting alloy, "Alnico 5," has become the standard of the industry. This paper describes the fundamental aspects of a procedure which can be used to further improve the properties of these anisotropic permanent magnet alloys. A study of the casting techniques used in the production of anisotropic Alnico permanent magnets indicated that the magnetic quality was affected by the as-cast macrostructure. Improved performance was observed in magnets containing a high percentage of columnar grains whose long axes were parallel to the magnetic axis of the casting. McCaig10 studied the effect of such columnar grain structures upon the magnetostriction characteristics of similar alloys, however no data was presented showing the effects on other magnetic properties. The following paragraphs describe two experiments which were conducted to determine the effect of various grain orientations upon the energy product. Special composite molds were prepared of highly conductive and highly refractive components to remove the heat of solidification from the casting in a controlled manner. Representative macrostructures produced by these techniques are shown in Fig. 1, along with the relative volumes of favorably oriented columnar grains. The alloy, Alnico 5, has the highest permanent magnet performance of any commercial magnet material. It has the nominal weight composition of 8 pct Al, 14 pct Ni, 24 pct Co, 3 pct Cu, and 51 pct Fe. A heat of this material was cast into molds producing the type A and B grain structures shown in Fig. 1 and pairs of the resulting magnets were placed in heat-treating boats so as to eliminate any biasing effects of boat position. After a standard heat treatment the type A magnets, with 16 pct of the volume composed of favorably aligned grains, had a maximum energy value of 3,940,000 gauss-oersteds, while the type B magnets with 73 pct aligned grains averaged 5,090,000. This large im-

Jan 1, 1954

By Thomas M. Drown

The use of bromine as an oxidizing agent, particularly for sul phur, has become very general in analysis, replacing the stronger oxidizing acids. The object of this paper is to describe briefly the experience which we have gained with this reagent in the laboratory of Lafayette College in the oxidation of metallic sulphides. Most of the simple sulphides, as blende, pyrite, etc., when exposed to the combined action of an alkaline hydrate and bromine, and finally to hydrochloric acid, are completely and promptly dissolved. The procedure is as follows: The very finely pulverized mineral is first treated, in a beaker, with a solution of sodium hydrate of a spe cific gravity of 1.25, and heated ; bromine is then cautiously added to supersaturation, and finally hydrochloric acid to acid reaction. If any of the sulphide is not taken up, the same operation may be re peated. It is necessary, however, that the mineral be very finely pulverized. Instead of using the pure bromine, a saturated solu tion of bromine in potassium bromide may be used with equally good effect. The process is advantageously simplified by making a saturated solution of bromine in the concentrated alkali. This is done by pouring bromine into a solution of sodium hydrate, of the above given specific gravity, until no more is taken up, and then adding a little of the sodium hydrate solution until the liquid does not give off free bromine. The procedure with this solution is as follows: The pulverized mineral is moistened with, say, 10 cc. of the solution, and heated, then hydrochloric acid added to just acid reaction. Two more additions of the alkaline solution, in amounts of 20 cc. each, are added at intervals of about ten minutes, each addition being followed by hydrochloric acid. The total amount of the alkaline solution (containing the bromine) used is, therefore, 50 cc., and the amount of hydrochloric acid should not exceed that necessary to make the solu tion acid after each addition of the alkali. The mixture should be kept hot. After the final addition of acid, the contents of the beaker is taken to dryness and heated in an air-bath to 110° to 115°C., to render silica insoluble. The dry mass is then taken up by hydro' chloric acid and water and, after filtration, the sulphuric acid is pre

Jan 1, 1880

By C. E. Shoenfelt

There was a notable decrease in drilling operations in 1940 in all of the Rocky Mountain states except Montana, where the two large fields on the Canadian border, Cut Bank and Kevin-Sunburst, were espe-cially active. The expanding markets for Montana natural gas made necessary the more intensive development of such fields as Rowdoin, Cedar Creek and Devon. While there were no important oil and gas discoveries in 1940 in any of the Rocky Mountain states, a few small pools were opened, which may constitute separate areas but may prove with later development to be extensions of old fields. Some of the old fields were extended and deeper pay zones were discovered in others. These have given the areas greatly increased oil reserves and therefore are just as important as the discovery of new fields. The more important of the developments in 1940 are given, by states, in the following paragraphs. Colorado Hiawatha Field, Moffat County.—The Mountain Fuel Supply Co. began the development at Hiawatha of its oil reserves, which were discovered in about 1929, and late in the summer oil began moving from the field by truck to the shipping point at Rock Springs, Wyoming. The Hiawatha field of northwestern Moffat County was discovered in 1927 by the Sormir Petroleum Co., with the completion of No. r Florence Wilson for 4,5,000,000 cu. ft. of gas a day from a Wasatch sand lens at 2200 it. In later development of the field, oil showings were reported in several wells but no development of this resource was undertaken until 1940, when a test of the oil possibilities was started with the release in April of a location for No. 5-A Wilson on the S\W. SW. NW. of sec. 23-1zN-1ooW., on the east side of the field. The Well had an initial production of 327 bbl. of oil a day pumping from three Wasatch (Tertiary) sands between 2005 and 2540 ft. It was drilled to 2562 ft., where the 65/8-in. casing was cemented and gun-perforated at 2005 to 2125 ft., 2260 to 2335 ft. and 2513 to 2540 ft. At the end of the year, this well was averaging zoo bbl. of oil per day, pumping. Two other wells were drilled for oil on Hiawatha during the summer—one a small well of 60 bbl. per day and the other a small gas well. Powder Wash Field, Moffat County.—The development of the Powder Wash field in northwestern Colorado was resumed in 1940 by the Mountain Fuel Supply Co., with the release of a location for No. 2-A Musser in the CWL.NW.SE. of sec. 4-1rN-97W. The Powder Wash field was discovered in 1931 by the Mountain Fuel Supply Co. and the discovery well, No. I Musser, on C.NW. of sec. 5-IIN-97W., was completed at 2152 ft. in the Hiawatha member of the nonmarine Wasatch for-mation for an open flow of 34,000,000 cu. ft. of gas per day under a natural pressure of 685 lb. per sq. inch. Oil was discovered in the Powder Wash field on Nov. 26, 1936, in the company's No. I Carl Allen on the NE.SW.SE. of sec. 32-12N-97W. The oil production was

Jan 1, 1941

By H. T. Matson

IN the Northern Rhodesia copper fields the size of the orebodies and the exceptionally consistent values over great distances made it possible to outline the ore with drill holes spaced at 1000-ft. intervals; in some cases, 2000-ft. intervals.. Owing to the fact that the size of the deposits made it very evident that much outside capital would have to be called in to develop them and, owing to the wide spacing of the holes, it was essential that the sampling of drill holes be as accurate as possible, so that outside examining engineers could adopt the results as trustworthy within the limits of accuracy of the drilling method. With this object in view, the field staffs of the Selection Trust group of companies have studied for the past three years, and are still studying, drill sampling in a very thorough manner, and for this reason it is felt that these notes may be of interest to engineers or students who are, or in the future may be, in charge of drilling operations. The orebodies in this field lie in shales and sandstones, more or less indurated, in the lower strata of the Roan series, and the copper mineralization is in the form of sulfides predominantly, with some oxidized copper minerals. Those interested in the geology and history of the area can find full details in a recent paper by Anton Gray and Russell J. Parker.1

Jan 1, 1930

By Otto Wartenweiler

After the phenomenal development of the new mine, the United Eastern Mining Co., with Mr. Frank A. Keith as President, decided to install a reduction plant. The character of the ore, closely resembling the product of other mines in the district, did not offer any particular metallurgical problems, since these neighboring mines had been operating milling plants very successfully for several years. Thus, with the general metallurgical treatment fairly well-defined, the matter of next importance was to design and construct a plant as economically as possible, that would give the best results obtainable. The ore consists of a mixture of calcite and quartz in about equal quantities, with some decomposed andesite, while the average value of mill feed was calculated to be $20 or more in gold, no silver being present. The tonnage to be treated at the start was fixed at 200 tons, but, in view of the favorable condition of the mine, it was considered advisable to arrange facilities for increasing the capacity to 400 tons. While it is best in some cases to adopt a distinct independent unit system where future enlargement is contemplated, in this instance the plans worked out differently. Summarized, the treatment adopted consists of coarse crushing, coarse grinding, fine grinding and cyanidation. For coarse crushing the selection of the No. 6 size gyratory crusher was governed not so much by its capacity as by the size of the feed openings to receive the run-of-mine material, which was too coarse for a No. 5 crusher. TO accomplish the coarse grinding to best advantage, a careful comparison was made between the modern steel ball-mill—the last word in crushing and grinding—and one of its older, and, at that time better-established, competitors, the rolls. The following conclusion was reached: While it is possible that for the sized plant under consideration the cost of operating rolls might be a little cheaper, it is preferable to use ball-mills because a simpler arrangement is possible, and because the handling of ball-mills is preferred by the operator. A marked departure was introduced for fine grinding. Instead of the long type of tube-mill, using pebbles, a mill of similar design was selected, but of much shorter length, using small cast-steel balls as grinding medium. For cyanidation, the Dorr continuous countercurrent process was

Jan 1, 1918

By J. H. Jackson, P. D. Frost, C. H. Lorig, A. C. Loonam

THIS paper describes (1) the effect of sodium on the tensile ductility of magnesium-lithium base alloys, and (2) the precautions necessary to avoid sodium contamination. Effect of Sodium on Properties The harmful effect of sodium in magnesium-lithium base alloys has been recognized by other investigators.1,2 However, quantitative data on its effect have not hitherto been published. The effect of sodium on the ductility of an 87 pct Mg-9 pct Li-4 pct Zn alloy is shown in fig. 1. The sodium was introduced by adding sodium chloride to the flux, which consisted of 50 pct LiC1-50 pct KC1. Moderately high ductility was obtained at an indicated sodium content of about 0.05 pct. Actually, the value probably was less than 0.05 pct, be-cause analyses of the lithium, which were more accurate than those of the alloy, indicated that the highest ductility was obtained when its sodium content was 0.02 pct or less. In fact, in alloys having somewhat greater strength than this particular composition, the sodium content of the lithium must be under 0.01 pct to avoid embrittlement. The effect of sodium on the ductility of several alloys having fairly low strength levels is shown in fig. 2. These alloys were melted with a flux containing 75 pct LiC1-25 pct LiF, to which various quantities of sodium chloride had been added. Sodium had no significant effect in pure magnesium but markedly decreased the ductility of the magnesium-lithium-zinc alloy, even though the alloy contained only 3 pct Li. As the lithium content of the binary alloys was increased, the ductility of the sodium-free alloys also increased. However, the effect of sodium on ductility became progressively more pronounced. Sodium raised the minimum hot-rolling temperatures, particularly those of the high-strength alloys, but its effect, in this respect, was less critical than its effect on tensile ductility. For optimum cold roll-ability, a low-sodium content was required. No deleterious effect of sodium on the stability of properties at slightly elevated temperatures was found. Control of Sodium in the Alloys Optimum ductility is obtained in the magnesium-lithium base alloys when sodium-free materials are used. Commercial lithium was formerly the chief source of contamination. Now purified lithium is usually available. When lithium of ordinary purity is used, the effects of sodium can be minimized by using a flux consisting of 75 pct LiC1-25 pct LiF. Bubbling nitrogen through the melt also helps remove sodium. The damaging influence of sodium on the ductility of the magnesium-lithium base alloys was observed very early in the alloy development program. The discovery came about as a result of chemical analyses made on the lithium used in the alloys. Ductile alloys had been made from lithium containing about 0.2 pct Na, whereas the lithium used in the brittle alloys contained about 0.9 pct Na. The first magnesium-lithium alloys were melted under commercial fluxes ordinarily used in melting magnesium alloys. These fluxes were unsuited for scavenging the contaminating sodium, and the resulting alloys were not ductile. Next, a flux containing 50 pct KC1-50 pct LiCl was tried. This was somewhat more effective but still was not satisfactory. After a number of different experimental fluxes had been investigated, one containing 75 pct LiC1-25 pct LiF was adopted. This flux made it possible to obtain good ductility in the alloys. The

Jan 1, 1951

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961