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By E. M. Kalar, I. Iwasaki, J. D. Zetterstrom

Several methods of removing fatty acid coatings from iron ore flotation concentrates were tested both on a Mesabi oxidized iron ore and on a magnetic taconite concentrate, and their effects on the duplex flotation process and on pelletizing were compared. Either acid or alkali alone could not remove the coatings, but a combination of such reagents as lime and quebracho, calcium chloride and pyrophosphate, or sulfuric acid and an organic acid (oxalic, malonic, or citric acid) was quite effective. The use of activated carbon was found to be particularly promising. The removal of fatty acid coatings from iron ores is of much practical interest when a pelletizing process is being considered for a concentrate floated with a fatty acid collector or when a duplex flotation process is being considered for upgrading an oxidized iron ore. A duplex flotation process is a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process is being used in the Florida phosphate fields.' Although in northern Michigan mills fatty acid flotation concentrates have been pelletized successfully, at other locations fatty acid coatings on iron flotation concentrates have proved so undesirable in the agglomeration operation that other methods of concentration had to be sought.' Since fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates, a combination of reagents, such as lime and quebracho,3 lime and alkali phosphate,4 or sulfuric acid and oxalic acid,' has been proposed. It was also thought that activated carbon might be effective in removing fatty acid coatings due to its high adsorptive capacity. Activated carbon, with its enormous surface per unit of volume, is well known for its exceptional efficiency in removing organic pollutants from industrial effluents. This article presents the practical aspects of the above methods when they are applied to the duplex flotation process and to the pelletizing of iron flotation concentrates. The article also includes a preliminary investigation of the common parameters involved in the depressant activity of the reagents. EXPERIMENTAL WORK Initially, the experimental work was directed towards the optimization of each method for the removal of hydrophobic coatings from iron oxide surfaces floated with fatty acids. Subsequently, the methods thus optimized were tested in the duplex flotation process with an oxidized iron ore and in the pelletizing process with a magnetic taconite concentrate. Preliminary Flotation Tests: Although the three types of chemical treatment reported in the literature were briefly investigated for the purpose of comparison, major emphasis was placed during the preliminary flotation tests on the use of activated carbon because it was thought to have certain advantages over the chemical methods. LIME AND QUEBRACHO - To obtain a flotation concentrate for optimizing the lime and quebracho method of fatty acid removal, the magnetic taconite concentrate was used. The concentrate had a size consist of 90% passing 325 mesh and analyzed 64.5% iron. After a few preliminary tests the fatty acid flotation procedure with the magnetic taconite concentrate was standardized as follows. A 1200-g sample of the magnetic concentrate was pulped in a Fagergren laboratoy flotation cell to 40% solids, conditioned with 0.5 lb of soda ash per ton for 2 min, and then further conditioned with 1.0 lb of Acintol FA-2 per ton for 2 min. After 5 min of flotation, recovery was nearly complete, averaging 98.6% of the weight and 98.7% of the iron. The cell product, which amounted to 1.4% by weight and analyzed 63.2% iron, consisted mainly of relatively coarse middling particles. Since the repro-ducibility of the flotation concentrates produced by this procedure was vey high, the same procedure was used to prepare fatty acid concentrates for each of the six tests of the lime and quebracho method. To test the removal of the fatty acid from the magnetite surfaces by the lime and quebracho method, a fatty acid froth product was returned to the flotation cell, repulped by 30 sec of agitation, and then con-

Jan 1, 1968

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By Robert K. Warner

When a new mine is opened, and often when an operating mine must adapt itself to physical or economic changes, a mining system must be selected in complete detail. In the past the plan chosen was usually the product of the local staff alone, however limited the training and experience of that staff might be, which often resulted in the introduction of methods that were familiar to the staff, but not so well suited to the conditions as others unknown to the local men. A new management, noting the difficulties with the existing layout, might make modifications or complete changes, so that many mines in their history have seen a whole series of mining systems, each somewhat laboriously grafted on to its predecessor. This should not be interpreted as a condemnation of the older staffs for sticking to the tried systems, such as open square-sets in the early days at the Homestake, because they knew it would work after a fashion, nor does the statement apply to the technically trained, and usually broadly experienced staffs of most present-day properties. The older miners did not have the variety of tools and methods, nor the present freedom of transfer of information as to what the other man is doing, and so did the best they could under the circumstances. Finally, the higher grade of the ores made the choice less vital. The ever-increasing need to mine low-grade orebodies, with a fixed or even lower price for the metal produced, has caused an increasing need for low-cost mining. In most new mines this has simplified the problem of selection by eliminating from consideration all of the high-cost systems, but it has also complicated the choice by the necessity for refinement in detail and a close adjustment of the plan selected to all the conditions at the property. In these low-cost problems any textbook division of mining systems as applied to "beds, veins or masses" avails little as a guide. It should be realized at the outset that to be successful under modern competitive conditions a system of mining must be worked out with elaborate detail, with careful time scheduling and control of the various elemental operations, and that after it is introduced it must be run with a large amount of technical direction.

Jan 1, 1934

By M. R. Hatfield, F. J. Vosburgh

In a recent article, it was shown that in the blast furnaces in Germany that are lined with carbon blocks no cooling plates are used, and that shower cooling is employed on the hearth and bosh sections. While one of the authors was in Germany he was told that one furnace was being operated without even the shower cooling on the bosh section, though the hearth section was shower-cooled. In discussion of this interesting situation with a number of blast-furnace operators in this country, it was made clearly and promptly evident that shower cooling was very unpopular, probably because of its messiness and its ineffectiveness. Both of the causes for the dislike of shower coolings are reasonable ones. Shower cooling can be and frequently is messy, but the present cooling of blast furnaces leaves much to be desired on that score. Shower cooling is ineffective as compared with plate cooling, so far as its usefulness in keeping the bricks cool enough not to melt or fall to pieces is concerned. However, the introduction of carbon linings changes the situation. No one is concerned with keeping a carbon lining cool, for no temperature in the blast furnace has any effect on carbon, which is just as stable at 3000°F. as it is at 70°F. The only concern is for the shell—to keep it cool enough for safety and comfort— and for that shower cooling is sufficient. Of course, with only the shell to cool, instead of the shell plus all the refractory material, much less water would be required, and the necessity for constant attention to the flow would be lessened, as the hundreds of inlets and outlets would be eliminated. Probably half of the water used in cooling a blast furnace is used for cooling the shaft and tuyeres and the remainder for the bosh and hearth sections. However, in view of the dislike of shower cooling in the United States, and particularly because at least one German blast furnace is operated with no cooling of the bosh section, thought was given to the possibility that a carbon-lined blast furnace might be operated without any cooling of the entire carbon-lined portion. For that reason a series of experiments was performed to determine what might be the temperature of the shell of a blast furnace protected by a carbon lining and operated under varying conditions up to a maximum inside temperature of 3000°F. Experimental Procedure A schematic diagram of the experimental setup is shown in Fig. I and a photograph of the entire assembly in Fig. 2. The heating element was a a tubc nominally 25/8 in. 0.d. by 2 in. i.d. by 30 in., used as a resistor. Power was furnished by a I5-kva. transformer operating

Jan 1, 1942

By M. R. Hatfield, F. J. Vosburgh

In a recent article, it was shown that in the blast furnaces in Germany that are lined with carbon blocks no cooling plates are used, and that shower cooling is employed on the hearth and bosh sections. While one of the authors was in Germany he was told that one furnace was being operated without even the shower cooling on the bosh section, though the hearth section was shower-cooled. In discussion of this interesting situation with a number of blast-furnace operators in this country, it was made clearly and promptly evident that shower cooling was very unpopular, probably because of its messiness and its ineffectiveness. Both of the causes for the dislike of shower coolings are reasonable ones. Shower cooling can be and frequently is messy, but the present cooling of blast furnaces leaves much to be desired on that score. Shower cooling is ineffective as compared with plate cooling, so far as its usefulness in keeping the bricks cool enough not to melt or fall to pieces is concerned. However, the introduction of carbon linings changes the situation. No one is concerned with keeping a carbon lining cool, for no temperature in the blast furnace has any effect on carbon, which is just as stable at 3000°F. as it is at 70°F. The only concern is for the shell—to keep it cool enough for safety and comfort— and for that shower cooling is sufficient. Of course, with only the shell to cool, instead of the shell plus all the refractory material, much less water would be required, and the necessity for constant attention to the flow would be lessened, as the hundreds of inlets and outlets would be eliminated. Probably half of the water used in cooling a blast furnace is used for cooling the shaft and tuyeres and the remainder for the bosh and hearth sections. However, in view of the dislike of shower cooling in the United States, and particularly because at least one German blast furnace is operated with no cooling of the bosh section, thought was given to the possibility that a carbon-lined blast furnace might be operated without any cooling of the entire carbon-lined portion. For that reason a series of experiments was performed to determine what might be the temperature of the shell of a blast furnace protected by a carbon lining and operated under varying conditions up to a maximum inside temperature of 3000°F. Experimental Procedure A schematic diagram of the experimental setup is shown in Fig. I and a photograph of the entire assembly in Fig. 2. The heating element was a a tubc nominally 25/8 in. 0.d. by 2 in. i.d. by 30 in., used as a resistor. Power was furnished by a I5-kva. transformer operating

Jan 1, 1942

By L. J. Buteau, R. E. Reed-Hill, W. A. Slippy

In a zirconium {1121} twins tend to have coherelzt boundaries and thus do not usually taper to a point when they intersect a grain boundary. Under the proper conditions, a (1121) twin may deform a boundary in such a manner as to clearly rcveal the twinning shear. Measurements of these grain-bounrlary rotatzons yield a value of 0.63 for the (1151) twinning shear. The magnitude of the observed shear and its shear sense are in excellent agreement with the assumption that the second undis-torted plme (K2) for this form of twinning is the basal plane (0002). The present value of the tzvinninz shear, which is approximately three limes larger than Rapperport&apos;s value? is in excellent agreement with reported results of Sokuskii and Prolsenko.5 RECENTLY westlake&apos; reported a study of the twinning modes of zirconium based on ~ap~er~ort&apos;s2 values for the twinning elements. He observed that two of the modes, (1012) and {1122), can be explained by relatively simple dislocation models. A workable model for (1121) twinning, however, proved to be very complex and questionable. Because Rapperport&apos;s second undistorted plane, (K2), for (1121) twinning has large indices, {ll2l6), it is possible that the difficulty in defining a model for (1121) twinning lies in an incorrect value for K2. A measurement of this twinning element has therefore been made, using a method based on observations of the shear displacement of grain boundaries at positions where they are intersected by (1121) twins. EXPERIMENTAL PROCEDURES The zirconium specimens were deformed in tension on an Instron machine either at the temperature of liquid nitrogen (77ºK), or prestrained at liquid nitrogen temperature and then further deformed at room temperature. Straining at 77°K was employed in order to nucleate (1 121) twins in large numbers, since simple ropm-temperature tensile deformation favors (1012) twinning. Specimens were machined from 1/2-in.-thick plate. The material was arc-melted sponge zirconium annealed to an ASTM grain size 4 and containing, in parts per million, 380 Fe, 880 0, <40 Hf, 32 N, and < 5 H. The specimen gage length and diameter were 1.25 and 0.130 in., respectively. To insure a gage section initially free of twins, the last 60 thousandths of the specimen diameter was removed by acid machining.

Jan 1, 1963

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By K. D. Hester, A. W. Fletcher

A nickel-copper sulphide concentrate was treated in a pilot plant at Warren Spring Laboratory during 1961, by a hydrometallurgical roast-leach-solvent extraction process devised to cleanly separate the metal values and produce acid sulphate liquors containing the metals. It is shown that 86 pct of the nickel and 95 pct of the copper could be leached from the calcine, after a sulphatizing roast on finely ground flotation concentrate. Iron was removed from the leach liquor by limestone neutralization with a small loss of values. Copper and nickel were separated by solvent extraction with naphthenic acid in kerosene after partial neutralization of the iron-free liquors with ammonium hydroxide. Hydrogen sulphide and chlorine were used to remove zinc (and residual copper) and cobalt impurities respectively. The recovery of pure copper and pure nickel, by electrowinning, from the acidic solvent extract strip liquors finally produced, appears technically feasible. An economic analysis of production costs shows that small, geographically isolated, nickel-copper sulphide deposits cannot usually be worked profitably by established processes. The requirements for profitable operation on a comparatively small scale could possibly be met by a flotation-roast-leach process. Two difficulties, obtaining satisfactory extraction of nickel from a sulphide concentrate and separating the copper and nickel in solution, have prevented the previous use of this method. A solution to the first problem, dissolution of the nickel, was described in a recent paper by Thornhill.1 It was shown in this paper that copper and nickel in a flotation concentrate could be oxidized to water soluble sulphates by roasting in a fluidized bed with added salt cake. Workers at the Warren Spring Laboratory have shown that the separation of copper and nickel can be accomplished by solvent extraction using a relatively inexpensive carboxylic acid, naphthenic acid. Moreover, the mineral acid required to strip values from the loaded solvent could be produced, and the metals recovered, by electrowinning; thus the latter section of the process was regenerative. The removal of iron from the leach liquor and the elimination of impurities such as zinc and cobalt before nickel electrowinning would be necessary to complete the flowsheet. The process under investigation could therefore be summarized (Fig. 1) as follows: 1) Flotation to produce a bulk sulphide concentrate. 2) Fluidized bed roasting to sulphate the nickel and copper minerals. 3) Leaching of roaster calcine to extract soluble nickel and copper. 4) Precipitation of iron from the separated leach liquor by air oxidation after the adjustment of pH and temperature. 5) Recovery of copper from the iron-free Liquor by pH adjustment and liquid-liquid extraction. 6) Purification of the copper raffinate by removing zinc and residual copper as insoluble sulphides and cobalt as cobaltic hydroxide. 7) Recovery of nickel from the purified liquor by pH adjustment and liquid-liquid extraction. Laboratory and pilot plant studies detailed below, were carried out at the Warren Spring Laboratory, to test the feasibility of each one of the unit processes and to obtain preliminary plant design data. FLOTATION The ore was an altered basic rock containing concentrations of magmatic sulphides.

Jan 1, 1964

By L. Weyher, H. L. Lovell

This discussion is restricted to a very specific application of the cyclone - its use as a hydro-cyclone in the cleaning of fine coal. It is hoped that the development of the present data will assist in the further elucidation of existing qualitative models, and also in an enhanced application of the hydrocyclone and provide a base for further research. Discussed are the mechanisms of gravity separation in hydro-cyclones, test procedures, experimental observations, and industrial applications from these studies. Within the general area of unit operations, a considerable effort has been expended in theoretical and empirical research associated with cyclone operations. The motivation involves the industrial requirement for devices and techniques to manipulate small particles at low operating costs, a situation required in coal preparation. There are good reasons why the cyclone helps to satisfy this demand, because it combines operational simplicity (no moving parts) with versatility and high throughput capacity per unit area. The cyclone is one of the most widely applied tools in the process technologies. There are areas for potential cyclone application which have been only meagerly explored or not considered at all. This discussion is restricted to a very specific application of the cyclone - its use as a hydrocyclone in the cleaning of fine coal. It represents an initial presentation of a more comprehensive report. Coal preparation can appropriately claim the hydrocyclone since most of its predominant industrial uses have originated in this area and have spread into other applications, including the broad field of ore dressing, the petroleum industry, chemical processing, nuclear engineering and food technology. There is one operational principle common in all cyclones: A fluid is tangentially introduced into a cylindrical or conical container under pressure. A predominantly irrotational flow field1 is established within the cyclone (Fig. 1). The uniqueness of this flow is indicated by the variation in tangential velocity across the cyclone radius, which reaches a maximum a short distance from the center and decays toward the cyclone wall. In contrast, the tangential velocity in a centrifuge increases uniformly toward the wall. Usually two products are discharged from the cyclone. They differ in that one discharge consists predominantly of that portion of the feed fluid which moves along the wall axially away from the feed inlet, while the other consists predominantly of fluid spiralling along the central regions of the cyclone, in an axial direction opposite to that of the wall current. Fig. 2 indicates these discharge points schematically. The latter product may be termed the vortex-product, since it is discharged with the central vortex-current. In the case of conical cyclones, the former product may be referred to as the apex-product. Although the names "over- and underflow" are widely used, many cyclones are operated from extreme angular positions thus the proposed terms are less ambiguous. The cyclone feed fluid can be laden with solid particles or nonmiscible fluid drops. Such a feed component is discharged from the cyclone, after some residence time, into the one or the other product. Yet, the orifice through which a particle will leave the cyclone is dependent upon a number of factors. These factors, in a statistical sense, determine the path of the particle within the cyclone. Thus, different separation phenomena are possible and different process results attainable by the controllable variation of the particle path. It is then, to attain a fuller understanding of this particle path, to which this study is ultimately directed. It is anticipated that the detailed study of the data being developed will allow further elucidation of existing qualitative models. However, the development of a quantitative description of cyclone operation in terms of a mechanism is not currently feasible. The flow conditions in a cyclone are not fully understood even for a pure fluid, without the added complexity of the inclusion of multiple size-density particles. It is hoped that the development of the present data will also assist in an enhanced application of the hydro-cyclone and provide a base for further research. Some practical applications drawn from the data are suggested. Cyclone operations have been classified according

Jan 1, 1967

By P. M. Blair, D. W. Peaceman

The shape and position of the gas-oil transition zone during downdip displacement of oil by gas has been calculated using flow equations which include the effects of gravity, relative permeability, capillary pressure and compressibility of the fluids. The calculations treat the problem in two space dimensions, and results are compared with data from a laboratory model tilted at 30° and 60° from the horizontal on displacements near and above the maximum rate at which gravity segregation prevents channeling of the gas along the top of the stratum. The good agreement between calculated and experimental results demonstrates the validity of the tecbnique as well as that of the flow equations. INTRODUCTION Knowledge of the fluid distribution and movement in an oil reservoir is important in producing operations and estimation of reserves. The history of the oil industry has included steady progress in improving the accuracy of calculations which provide the required knowledge. The earliest method of calculating reservoir performance consisted of material-balance equations based on the assumption that all properties were uniform throughout a reservoir.l For many reservoirs such a simple formulation is still the most useful. However, when large pressure and saturation gradients exist in a reservoir, the assumption of uniform values throughout may lead to significant error. To reduce these errors, Buckley and Leverett2 introduced a displacement eqation which considers pressure and saturation gradients. Methods available at that time permitted solutions to the Buckley-Leverett equation in one space dimension; these solutions have been very useful in solving many problems related to the production of oil. However, the one-dimensional methods are not adequate for systems in which saturations vary in directions other than the direction of flow. An example of such a system is the case of gas displacing oil down a dipping stratum in which the gas-oil contact becomes significantly tilted. Of course, the Buckley-Leverett displacement method cannot predict the tilt of the gas-oil contact. Recent improvements3,4 of the one-dimensional Buckley-Leverett method achieve some success in predicting the tilt of the gas-oil contact at sufficiently low flow rates. However, at rates high enough that the viscous pressye gradient nearly equals or exceeds the gravity gradient, even these improved one-dimen,sional methods incorrectly predict the shape and velocity of the contact. Further progress in estimating such fluid movements in a reservoir appears to require consideration of the problem in more than one space dimension. The recent two-dimensional method of Douglas, Peaceman and Rachford5 appears adaptable to calculate changes with time of the saturation distribution in a vertical cross-section of a reservoir. The movement of saturation contours should represent the moving fluid contacts and include the effects of crossflow due to gravity, as well as variations in the rock and fluid properties. The nonlinear nature of the equations used in the method has prevented proof of the validity of the solutions. Douglas, Peaceman and Rachford made some comparisons with experiment but did not include cases in which gravity was important nor cases involving displacement by the nonwetting phase.For these reasons, a test of the two-dimensional method for a case in which these factors are included would be very desirable. The test selected was a comparison of calculated results with those from a carefully controlled laboratory experiment on a model with measured physical properties. The model selected was one in which gas displaced oil down a tilted, rectangular sand pack. The model can be thought of as representing a vertical cross-section taken parallel to the dip of a reservoir. The displacement thus simulates gas displacing oil downdip that might result from gas-cap expansion or gas injection. This report outlines the calculation method used

By R. B. Schluter, M. M. Fine

The Bureau of Mines&apos; Twin Cities Metallurgy Research Center has of late concerned itself with reduction-induration of iron ore. One development provided a flowsheet for the agglomeration of green concentrate pellets in a reducing atmosphere created by a solid reductant external to the agglomerate. The product pellets were well metallized and physically competent. Maximum recommended operating temperature was 2100º F. In these studies, it was observed that unflred iron ore pellets indurated in a bed of anthracite or certain lignite chars frequently acquired exceptional crushing strength. A diagnosis of the phenomenon revealed that sulfur in the fuel was the probable cause. Accordingly, a research program was established to test this premise and to put it to practical use. Gaseous reductants were employed initially because of the ease and accuracy with which they could be metered.

Jan 10, 1969

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood&apos; suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener&apos;s mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh&apos;s5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By Frederic Benard

The treatment of Balbach-Thum slimes at Copper Cliff by the Ontario Refining Co, is of interest because it differs considerably from methods usually employed for the recovery of fine gold from parting-plant slimes. Owing to the comparatively high percentages of palladium and platinum, wet methods are used to remover the greater proportion of these metals before electrolytic refining in the Wohlwill cells. The Plant The platinum-metals department, Wohlwill room, and gold-melting room extend along the north side of the silver refinery and are separated from the parting plant by a glass partition (Figs. 1 and 2). The platinum-metals department resembles a laboratory built on a large scale, with the various pieces of equipment laid out on terraces to facilitate handling. Because of the corrosive nature of the solutions, chemical stoneware is used throughout. Elevation of acids is accomplished by means of Mariotte bottles. On the top level are three steam-jacketed stoneware kettles of 50-gal. capacity, also a packed tower. One kettle is used for digesting the slimes while the remaining kettles are used for precipitating the gold. The dissolver is equippcd with a treated concrete hood, which is connected to the flue system. Gases are drawn off through the packed tower by means of a 6-in. stoneware exhaust fan. A 15 per cent solution of sodium carbonate is continually circulated through the tower. On the intermediate level are two suition filters, one for removing silver chloride and the other for the gold sand. The filter medium consists of an asbestos pad covered with a filter paper on which is a layer of twill. On the bottom level are two rectangular cementation tanks, 24 by 48 by 24 in. deep, and a suction filter used for removing the platinum-metal concentrates. The circulating pump for the packed tower is also here. Suction is provided by a vacuum pump having a capacity of 8 cu. ft. at 20-in. vacuum.

Jan 1, 1944

By Norman D. Fitz Gerald

The lack of a continuous operating balance in petroleum refining, which is analyzed in this paper, is by no means a feature solely of this division of the oil industry. Serious disequilibria of a capital as well as an operating nature exist both in the producing and marketing departments, while problems in the former and to some degree the latter are complicated by political involvements. Attention has previously been directed to the unstabilizing influence of present proration formulas in stimulating unnecessary drilling.&apos; While equilibrium in petroleum refining operations has been fairly well maintained in the past decade, examination of departures may prove fruitful. Economic analysis is the application of time and motion study to the functioning of management, rather than labor. Properly applied it may reveal changes in policies that would increase the utility of the properties and facilities of the industry for stockholders, employees and the public, while contributing a stabilizing influence to the general economy. The study of economic equilibrium is essentially one of measurement and interpretation, requiring adequate data and the development of a technique of analysis that employs statistical and mathematical methods as a supplement to the broad descriptive phase of economics. Economic equilibrium in petroleum refining is a dual concept. It embraces both the over-all balance between total storage and total demand for major products and the internal balance between the demands and inventories of the various products. The latter is the more complex of the two for it is concerned with proportionating the supplies of the several products stemming from the joint source to the demands for the individual products which are subject to wide variations. All the products are essentially nondurable goods, and they are used both by producers and consumers but in varying proportions. Motor fuel is very largely a consumer&apos;s good, while residual fuel oil is almost entirely a producer&apos;s good, the other products falling between these extremes. The peculiar-

Jan 1, 1939

By Norman D. Fitz Gerald

The lack of a continuous operating balance in petroleum refining, which is analyzed in this paper, is by no means a feature solely of this division of the oil industry. Serious disequilibria of a capital as well as an operating nature exist both in the producing and marketing departments, while problems in the former and to some degree the latter are complicated by political involvements. Attention has previously been directed to the unstabilizing influence of present proration formulas in stimulating unnecessary drilling.&apos; While equilibrium in petroleum refining operations has been fairly well maintained in the past decade, examination of departures may prove fruitful. Economic analysis is the application of time and motion study to the functioning of management, rather than labor. Properly applied it may reveal changes in policies that would increase the utility of the properties and facilities of the industry for stockholders, employees and the public, while contributing a stabilizing influence to the general economy. The study of economic equilibrium is essentially one of measurement and interpretation, requiring adequate data and the development of a technique of analysis that employs statistical and mathematical methods as a supplement to the broad descriptive phase of economics. Economic equilibrium in petroleum refining is a dual concept. It embraces both the over-all balance between total storage and total demand for major products and the internal balance between the demands and inventories of the various products. The latter is the more complex of the two for it is concerned with proportionating the supplies of the several products stemming from the joint source to the demands for the individual products which are subject to wide variations. All the products are essentially nondurable goods, and they are used both by producers and consumers but in varying proportions. Motor fuel is very largely a consumer&apos;s good, while residual fuel oil is almost entirely a producer&apos;s good, the other products falling between these extremes. The peculiar-

Jan 1, 1939

By C. P. Besse, G. W. Osborne

Drilling operations on the Gulf of Mexico continental shelf are following two general plans. The first plan placed all buildings. equipment, and materials on a large platform while the second copies Lake Maracaibo drilling methods by placing a minimum of equipment on the platform and using a floating drilling tender or drill barge anchored adjacent to the platform in an attempt to take maximum advantage of flotation in an effort to reduce costs. A complete power rig, mud pits, pipe racks, and small auxiliaries have been placed on the platform as shown in Figure 1, to assure proper handling of drilling operations under the most adverse weather. This has the economic advantages of eliminating the fabrication of a large structure, a material reduction of rigging up time on each structure. and elimination of delay time on equipment while quarters and equipment placed on the tender are being rigged up. These factors have certainly proved their economic value in drill barge operations in the Louisiana and Texas coastal area. Naturally the heart of such an operation is the anchorage. This anchorage, to permit taking advantage of maximum economies. must hold the ship in a relatively fixed position under the following weather conditions: (1) Winter northwesters (2) Southeasterly gales (3) Severe rain squalls In hurricane weather all operations must be suspended regardless of method of operation and the floating tender will, if possible, be moved to a protected location. However, in case of an emergency the floating tender should be prepared to swing with the wind and seas on a single anchor as there is considerable doubt that either ship or anchorage could withstand the severe strains imposed by fixed anchorage in hurricane weather. Northwesters are reported to have developed wind gust velocities as high as sixty miles per hour and steady winds of approximately forty-five miles per hour. Fortunately these winds do not travel a great distance over water before arriving at our location, and, while they can possibly develop seas approximately eight feet high, the waves are short, and if taken on the bow or stern of a ship 250 feet or more in length they should not present a difficult problem. On the other hand southeast gales having a long fetch and maximum steady wind velocities of approximately thirty miles per hour can possibly develop long swells approximately twelve feet in height. These should develop the most severe anchorage problem. To combat these waves any workable anchorage plan should permit maneuvering the ship in such a manner as to head the bow or the stern into the seas and still maintain contact with the structure. Rain squalls develop wind gust velocities as great as sixty miles per hour. However, they are local and the seas have not been a source of great trouble. To permit continuous operation the anchorage must be able to withstand these winds broadside to the ship as the wind direction often changes radically in a very sliort time. All of these weather conditions are dangerous to small craft, deck cargoes,

Jan 1, 1949

By C. P. Besse, G. W. Osborne

Drilling operations on the Gulf of Mexico continental shelf are following two general plans. The first plan placed all buildings. equipment, and materials on a large platform while the second copies Lake Maracaibo drilling methods by placing a minimum of equipment on the platform and using a floating drilling tender or drill barge anchored adjacent to the platform in an attempt to take maximum advantage of flotation in an effort to reduce costs. A complete power rig, mud pits, pipe racks, and small auxiliaries have been placed on the platform as shown in Figure 1, to assure proper handling of drilling operations under the most adverse weather. This has the economic advantages of eliminating the fabrication of a large structure, a material reduction of rigging up time on each structure. and elimination of delay time on equipment while quarters and equipment placed on the tender are being rigged up. These factors have certainly proved their economic value in drill barge operations in the Louisiana and Texas coastal area. Naturally the heart of such an operation is the anchorage. This anchorage, to permit taking advantage of maximum economies. must hold the ship in a relatively fixed position under the following weather conditions: (1) Winter northwesters (2) Southeasterly gales (3) Severe rain squalls In hurricane weather all operations must be suspended regardless of method of operation and the floating tender will, if possible, be moved to a protected location. However, in case of an emergency the floating tender should be prepared to swing with the wind and seas on a single anchor as there is considerable doubt that either ship or anchorage could withstand the severe strains imposed by fixed anchorage in hurricane weather. Northwesters are reported to have developed wind gust velocities as high as sixty miles per hour and steady winds of approximately forty-five miles per hour. Fortunately these winds do not travel a great distance over water before arriving at our location, and, while they can possibly develop seas approximately eight feet high, the waves are short, and if taken on the bow or stern of a ship 250 feet or more in length they should not present a difficult problem. On the other hand southeast gales having a long fetch and maximum steady wind velocities of approximately thirty miles per hour can possibly develop long swells approximately twelve feet in height. These should develop the most severe anchorage problem. To combat these waves any workable anchorage plan should permit maneuvering the ship in such a manner as to head the bow or the stern into the seas and still maintain contact with the structure. Rain squalls develop wind gust velocities as great as sixty miles per hour. However, they are local and the seas have not been a source of great trouble. To permit continuous operation the anchorage must be able to withstand these winds broadside to the ship as the wind direction often changes radically in a very sliort time. All of these weather conditions are dangerous to small craft, deck cargoes,

Jan 1, 1949

By G. Y. Chin, A. R. Von Neida

The relationship between crystalline texture and magnetic anisotropy in a Co-10 pct Fe alloy has been investigated by means of X-ray pole .figures, hysteresis-loop tracings, and magnetic-torque measurements. The cold-rolled texture of a sample after 95 pct thickness reduction is of the "brass-type", that is, (110)[112/. At 500°C the cold-rolled material recrystallizes fo a (311)[112] orientation, plus a minor (210) [001] component. This texture persists up to 1400°C, at which point it is replaced by a secondary recrystallization texture, (111)[112]. Magnetic-torque measurements show that the easy axis of magnetization lies along the transverse direction in the cold-rolled material and changes to the rolling direction after primary recrystallization. This change is also reflected in the hysteresis characteristic; whereas the B-H loop along the rolling direction is nonsqunre with a low value of residual induction (750 vs 19,000 gauss at saturation) for the cold-rolled material, the annealed sample exhibits a very square loop with a large value of residual induction (16,000 gauss). Theoretical torque curves calculated from the texture data on the basis of magnetocystalline anisotropy energy compare favorably with the observed torque curves. Values of the crystal anisotropy constant, K1, obbained from these comparisons are in good quantitative agreement with single-crystal data. Furthermore, both the torque amplitude of the poly crystalline material and the magnitude of K1 obtained with a single crystal show an identical temperature dependence over the range from —195° 10 +220°C. It is thus conclzided that the magnetocrystalline anisotrpopy erlergy is chiefly I-esponsible. for the nzagnetic allisotropy of textured Co-10 pct Fe alloy. THE results of a study on the relationship between crystalline texture and magnetic anisotropy of an alloy containing 90 pct Co and 10 pct Fe by weight are reported in this paper. The alloy has an fcc structure: a saturation magnetization of about 19,000 gauss,2 and a nearly zero value of magnetoatriction.3 puzey4 has reported a large crystalline anisotropy constant of -7.4 X 105 ergs per cu cm, indicating the (111) directions as the easy axes of magnetization. Hence, texture variations resulting from cold work and annealing are expected to introduce a magnetic anisotropy in the polycrystalline material through the alignment of these (111) easy directions. In the present study, magnetic anisotropy of both rolled and annealed strips was determined by magnetic-torque measurements and hysteresis-loop tracings The results were correlated quantitatively with calculations based on texture data obtained by the X-ray pole-figure technique. It is established that the magnetocrystalline anisotropy energy is indeed chiefly responsible for the magnetic anisotropy of textured Co-10 pct Fe alloy. EXPERIMENTAL Material Preparation. The alloy nominally contained 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn by weight, the chief impurities being nickel, carbon, and silicon (less than 0.5 pct total). The cast ingot was rolled to strips 10 mils thick and slit to 1 in. in width. After strand annealing at 900°C in a hydrogen atmosphere, these strips were further cold-rolled to various thicknesses down to 0.25 mil (97.5 pct reduction), with samples collected for study of the development of texture and magnetic anisotropy as a function of thickness reduction. subsequently, samples cold-rolled from 100 mils to 0.25 mil were obtained, thus extending the thickness reduction range to 99.75 pct. In addition, 0.5-mil samples cold-rolled from 10 mils were selected

Jan 1, 1965

By A. J. Teplitz, T. Bardeen

In the course of an investigation of lost circulation, a new tool has been developed which gives a qualitative measure of the relative velocity between the fluid column in the borehole and the tool. The position of a diaphragm in the side wall of the instrument depends on the flow through the device. This position is established by using the conductive borehole fluid in a potentiometric circuit. The instrument has high sensitivity and can detect changes in velocity as low as. 5 ft/min. Lost circulation mud additives do not interfere with the satisfactory performance of the tool. In a number of circulation losses of the pressure induced type, the instrument has shown that the losses were confined to extremely narrow zones (less than I ft), indicating that such ruptures occur in a more or less horizontal rather than vertical plane as has often been assumed. This pinpointing of the zone of loss is important in remedial procedures since it allows the treatment to be applied directly to the point of loss rather than to the entire open hole. The device can also be employed for indicating points of entry of water in producing wells. INTRODUCTION The need for an improved means of locating the positions of lost returns zones became evident during an investigation of lost circulation difficulties in the Gulf Coast area.1 With instrumentation available at the time, it had been learned that, contrary to common belief, the position of the thief zone responsible for a given loss seldom coincided with the point of bit penetration at the time the loss was encountered. In the majority of cases, the losses were found to be occurring at some distance removed from the bottom of the hole —sometimes as much as a few thousand feet. This information, along with other observations made during the investigation, led to improved techniques&apos; for dealing with lost circulation problems. Highlighted, however, among the results of this work and of similar studies subsequently conducted in drilling operations in other parts of the country, was the indication that a considerable portion of the difficulty and expense involved in treating prolonged circulation losses is due to the unsystematic application of remedial measures to one or more apertures of unknown position. Basis of Tests It is worth considering that if the troublesome formation could somehow be transported to the surface where it could be directly observed, there would likely be little difficulty in readily effecting a seal. Although this is a decided oversimplification of the situation, it does appear that the chief obstacles to similar ease of handling of a lost circulation zone in a well are lack of visibility and of ready accessibility. The latter handicap is overcome to a considerable extent by placement techniques already in use, and other procedures now in the process of development are expected to offer further improvement. But in the matter of visual observation, the technique to be presently described appears to afford a quite satisfactory substitute.

Jan 1, 1957

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler&apos; and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970