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By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955

By John V. Beall

Given: One large, but dated open-pit copper mine and processing plants, down about one third in production capacity in decade because of declining ore grade. Solve for: Restoration of former peak capacity without further losses during period of reconstruction. That is the problem that Kennecott's Utah Cop- per Division began solving in 1963. Most of the work went to a task force of engineers, several of whom were plucked out of line jobs and assigned to the so-called "Expansion Project" for the duration. There was no doubt from the beginning that effective cooperation between Expansion Project engineers and operators was critical to success, and personnel was chosen accordingly. This foresight paid off. The Expansion Project is all but complete, and the Utah Copper Division is returning to its rated capacity of 300,000 tons per year of copper metal.

Jan 6, 1967

By C. E. Julihn

Technology concerns the ways of doing things; mineral technology the ways of performing operations required for obtaining minerals from the earth and extracting their valuable constituents for man's use. At any particular time, technology is relatively fixed, as everyone tries to adopt the way of doing things that has proved most profitable; but improvements evolve from minor changes here and there, and occasion- ally entirely new methods are discovered. Technologic improvement thus characterizes any long-time view of the mineral industries. Its test lies always in reduction of costs; there is no other incentive for the adoption of new methods. Reduction in cost of producing metal from ore decreases, in turn, the amount of metal that must be obtained from ore in order to pay for its production. An advancing technology thus is characterized by utilization of ores of lower and lower grade. A very important result of this is an increase in the gross quantity of metal obtainable at any price level, since the earth's crust contains vast amounts of very low-grade ores and relatively insignificant amounts of very high-grade ores. Technologic advances have, therefore, been the means of rendering the metals both cheap and abundant. Though concern as to possible exhaustion of the world's ore deposits is warranted, it is conceivable that a transcendent technology of the future might supply metal requirements from what we

Jan 1, 1932

By Carl Zapffe

The manganese ore reserves of Lake Superior, because of their location and nature, have recently achieved a rnarked degree of importance as compared with the world's manganese reserves. To appreciate fully the significance and the adequacy of this reserve, one should understand how such ores are used, where obtainable, the quantity used, possible avenues for increasing use or application, and the chemical and physical characteristics of the available ores. Only with those data at hand, is it possible to arrive at a convincing answer to the question whether the reserves of manganiferous iron ores are adequate to satisfy the annual demand of the presently known iron ores for the full life of the latter. That they should last is vital; and to ascertain whether they will last was the purpose of the present investigation, which marks the first attempt to study these Lake Superior reserves. The Lake Superior region possesses and supplies the full assortment of iron ores needed for the conversion of ore into pig iron and steel ingots and castings. These ores are named bessemer, low-phosphorus and high-phosphorus non-bessemer, manganiferous and siliceous; and to include the term aluminiferous would be in keeping with the most recent nomenclature adopted by some dealers. About 35 or 40 years ago, perhaps less, most of the Lake Superior ore which is being used today was the material then considered either useless or too poor for immediate use; perhaps it was considered no more than a future reserve. An examination of the analyses of ores and the guarantees in the sales of those older times convince one that the opinions of those days must have been governed by only small differences in analyses. Some grades of ores used today in substantial amounts were used most sparingly only one or two decades ago. The relative quantities of the different ores used are ever changing; and, bit by bit, the metallurgy and the opinions are ever changing and the prejudices against certain ores and practices decrease. This is unquestionably more pronounced for the manganiferous ores than for any other kind. If, when using the present data for manganiferous ores, we will only be content to make allowances for the same experiences other kinds of ores

Jan 1, 1927

By Margaret Dienes, Karl L. Fetters

IT is recognized that ingot structure is important in determining the quality of finished steel. Such elements of ingot structure as the size, shape and distribution of primary crystals; the size, shape and distribution of shrinkage cavities; the degree and kind of segregation (both macro and micro); the distribution of nonmetallic impurities and gas cavities are each the result of solidification phenomena. These structural features vary with variations in ingot practice: Their control requires a knowledge of their correlation with the variables of ingot practice. The structures of full-sized commercial steel ingots have been studied extensively by the Steel Ingots Committee of the Iron and Steel Institute.1 This work has contributed much to our knowledge of ingot structure and the factors that control it. These investigations of necessity have been limited in scope because of their costliness and the great amount of time required. Studies of the structure of small steel ingots have not been very satisfactory because of the rapid rate of freezing of the ingots. Their structures are thus difficult to resolve and to interpret. Medium sizes of steel ingots in the ranges of 150 to 500 lb. do offer opportunity for study, but their cost also becomes greater and their use less expeditious. Experimental models for the study of steel-ingot structure have been made of nonferrous metals. Gathmann2 used lead-tin alloys and reported that they were satisfactory for determination of the location of the major shrinkage cavities and the "planes of weakness" resulting from the pattern of crystallization. Certain features of mold design have been illustrated by these results. Bezdenezhnihk3 has used copper and aluminum ingots similarly and has shown the effect of mold-wall thickness on the depth of columnar grains. These studies of nonferrous models have been useful, but their results have been limited because the analogy with steel ingots obviously is not a close one. Model wax ingots have also been useful in pointing out important features of mold design. Gathmann4 watched the solidification of wax ingots, through a glass-walled mold, and has reported the effects of mold type on the location of the shrinkage cavities. Segregation was simulated by using a mixture of paraffin and stearine and adding a red dye that on freezing segregated preferentially to the stearine. Brearley5 also used wax models to determine .the effects of some of the principal features of mold design. Carlsson and Hultgren6 used stearic acid to show that the columnar crystals of ingots tend to slope upward progressively from the mold wall toward the center of the ingot. As with the nonferrous ingots, the wax ingots have

Jan 1, 1943

By P. Shahinian, J. Weertman

Minimum creep rates of nickel samples were measured in the stress region of 2.5x107 to 2.8xl0 dyne per sq cm and the temperature region of 400° to 1100°C. The creep rate seems to be proportional to (stress) at stresses below 7x10H dyne per sq cm. The activation energy of creep is approximately 65,000 cal per mol. IN a recent theory' of steady-state creep which is based on Mott's dislocation climb mechanism, the following creep equation was derived for creep in polycrystalline metals (if where K is creep rate, Q the activation energy of self-diffusion, S the entropy of activation of self-diffusion, L' the grain size, L the subgrain size, b the length of the Burgers' vector of a dislocation, u the shear modulus, u the stress, a the critical shear stress, M the density of active Frank-Read sources, v the vibrational frequency of a vacancy, and kT has its usual meaning. This equation predicts a creep rate which depends on the stress through a power law at low stresses. At high stresses the creep rate increases much more rapidly with stress. The theory breaks down for stresses great enough that the inequality holds true. It was the purpose of the present in-

Jan 1, 1957

By A. P. Young, L. I. Marsh

HE relationship between microstructure and *- fracture is of interest in many metals and alloys. This relationship is sometimes established by examining the fracture surfaces and the flat surfaces near the fracture path in tensile samples. However, it is often difficult to tell from examining the fractured sample whether the fracture is intergranular, intra-granular, or a mixture of both. Also, it is often of interest to follow the progress of slip, twinning, or crack formation along the fracture path before fracture occurs. The ambiguity concerning the type of fracture generally can be resolved if the area along the path of ultimate fracture can be photographed at inter-

Jan 1, 1959

By Andrews Allen

THE large increase in the wages of mine workers makes it imperative that all factors tending to limit production per miner be eliminated, if possible. The trolley and storage-battery locomotive, mining machine, hoisting engine, mining system, etc. have increased the possible output per man. But this output is still limited by the capacity of the hoisting engine and cable and by the size of the mine car. The superiority of skip hoisting in metal mining is shown by its almost universal adoption. By varying the size of skip and the rope speed, any desired hoisting tonnage can be secured and, since only one kind of material is handled and breakage is unimportant, the loading of the skips can be easily and cheaply effected from bins into which the cars are dumped. The cars may then be designed to fit the conditions in the mine instead of being a compromise between hoisting and mining conditions, very likely suiting neither. In coal mines, the usual practice has been to hoist the car to the surface, either on platform or self-dumping cages. Of late years the number of skip-hoisting plants in coal mines has been rapidly increasing, but there is more or less inertia to overcome in establishing so radical a change in practice; also the earlier skip operations were not uniformly successful. As a result, it became evident that metal-mining practice would require radical modification before skip hoisting could be successfully used in coal mining.

Jan 2, 1921

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By Richard S. McCaffery, Clarence H. Lorig, Joseph F. Oesterle, Ira N. Goff, Oscar O. Fritsche

This paper is the report of an investigation to determine the relations between the viscosity, temperature and composition of that portion of the silica-alumina-lime-magnesia system(l) within which blast-furnace slags are found. The work reported in this paper was made possible by a grant of funds from Engineering Foundation. It is a part of a project, the determination of properties and structure of iron blast-furnace slags, upon which the laboratories of the University of Wisconsin have been at work for some years. Three papers have been published, which have marked the progress of the study of iron blast-furnace slags at Wisconsin. The first,(2) Desul-furizing Power of Iron Blast-furnace Slags, discussed the solubility of sulfur in slags that contained no magnesia and discussed the viscosity. The second, (3) The Constitution of Iron Blast-furnace Slags, developed the constitutions of slags in the four-component system, silica-alumina-lime-magnesia, and pointed out an explanation of slag structure. Composition of Iron Blast-furnace Slags,(l) which was the third paper, gave a method of calculating the percentages of the various compounds present in slags when the amount of oxide was given and also an interpretation of quaternary equilibrium. Illustrations were given of the mineral composition of blast-furnace slags and some applications of composition results were shown. Because of their relative ease of measurement, the viscosity-temperature relation for slags was selected as a factor which would be useful in correlating the physical properties of molten slags to furnace operation. With this in mind the viscosities of slags whose compositions are in that portion of the quaternary system, silica-alumina-lime-magnesia, in which blast-furnace slags occur, were thoroughly investigated.

Jan 1, 1932

By J. W. King

URANIUM ore was first discovered in the Edge-mont district of the southern Black Hills in the summer of 1951. The discovery was not made known for some time, but after the news leaked out prospecting became intense, and several hundred claims were staked in the spring of 1952. The Hot Springs Sub Office of the Atomic Energy Commission was established at that time and airborne radiometric surveys were commenced by the Government and by private companies. During the succeeding summer another important discovery was made by private airborne surveys in the northern Black Hills, and the area favorable for uranium ore was expanded many times. Between that summer of 1952 and the present, many individuals and groups have explored, developed, and exploited their claims until now uranium ore is produced in significant quantities and substantial reserves have been developed. The Black Hills portion of the geologic map of the U. S. issued by the U. S. Geological Survey is shown in Fig. 1. Sedimentary formations are exposed as a series of cuestas and hogbacks in a roughly annular pattern with the older sediments resting on the pre-Cambrian core, which is exposed in the eastern and southern portions of the dome. The South Dakota-Wyoming state line bisects the area from north to south. The Cheyenne River crosses the southern tip of the Black Hills and the Little Missouri bounds them roughly on the north. Headquarters of the AEC in the Black Hills is the Sub Office at Hot Springs, S. D. An ore buying station is located in Edgemont, 28 miles to the southwest, where a mill is presently under construction. The area of original uranium ore discovery and of principal activity in the southern Hills is a few miles north of Edgemont. Several areas of anomalous radioactivity have been noted between Dewey, S. D., and Newcastle, Wyo. A limited amount of ore has come from the Dewey area and private exploration is active there. The Carlile deposit, largest producing mine in the northern Black Hills to date, lies northwest of the Belle Fourche River near the western extremity of the Hills. Two of the larger known orebodies of the area are located near the Little Missouri River where a small window exposes the favorable strati-graphic horizon of the Fall River sandstone. Small production has recently come from Barlow Canyon, near Devils Tower, Wyo., Fig. 2, and numerous areas of anomalous radioactivity are known in the vicinity. Three producing deposits and scattered radioactivity are found along the state line east of Aladdin, Wyo. Several areas of weakly anomalous radio-

Jan 1, 1957

By A. J. Lynch, E. V. Manlapig, J. S. Hall, G. C. Thorne

Modelling of industrial sulphide flotation based on data collected in several flotation plants is discussed. A mechanistic approach is used in which it is recognised that flotation is a two stage pro- cess with concentration occurring both in the pulp and in the froth. The important features of the model, which is a kinetic model, are – 1. for each particle species there is a range of flotation rates which corresponds to the range of particle sizes, 2. the flotation rates of the liberated gangue particles which have no hydrophobic properties are dependent on the flotation rate of water and are controlled by variables such as the air and frother addition rates, and the pulp level, 3. as an approximation the valuable sulphide particles may be regarded as being present in two groups with high and low flotation rate constants, 4. increase in the addition rate of collector tends to increase the proportion of sulphide particles which are in the high flotation rate constant group. The actual flotation rate of each group of particles is a combination of an "inherent" flotation rate and a flotation rate which is dependent on the flotation rate of water, 5. at particular air and frother addition rates and pulp levels there is a physical limit to the rate at which particles can be transported into the concentrate and this is recognised in the model. The model has been used to study the steady state and dynamic properties of flotation circuits in operating plants. The assessment of the behaviour of composite particles is difficult because of the problem of quantitatively describing the surfaces of mineral particles. A method which is being developed to measure unpolished particles is described briefly.

Jan 1, 1976

By John T. Ryan

FOR the first ten months of 1942, on which data are available at the time this is written, the coal-mining industry achieved a most creditable safety record, and ha1 figures for the year may show a record surpassing that of 1941 in which the industry reached the best accident rate in its history. The ten- month accident rate for both bituminous and anthracite mining in 1942 was 2.197 fatalities per million tons of coal mined, compared with a revised rate of 2.271 for the same months of 1941. The bituminous rate decreased from 2.139 in 1941 to 2.039 for ten months of this year, and the anthracite rate shows a reduction from 3.707 to 3.699 for the same period.

Jan 1, 1943

By F. A. Forward, V. N. Mackiw

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting copper, nickel, cobalt, and sulphur from high grade nickel concentrate produced from Lynn Lake ores, and describes in some detail the chemistry of the process. IT is well known'.' 2 that copper, nickel, cobalt, zinc, ferrous iron, and a number of other metals combine with ammonia in aqueous solution to form complex ions of the form [Me(NH,)x]"+. The stability and solubility of these ions depend on the concentration of the metal ion in solution, on the amount of NH, present, and on the amount and type of anions present, e.g., OH-, C0;-, NO,, C1-, SO;-. If ammonia is partially or completely removed from such solutions, for example by boiling, the soluble ammines tend to decompose and the metals precipitate as basic salts. These properties of metal ammines have found practical application in the commercial recovery of copper, nickel, and cobalt from a variety of ores. In an operation formerly conducted at Kennecott"" the mill tailing containing 0.80 pct Cu as copper carbonate was leached by percolation with an ammonia-ammonium carbonate solution to dissolve the copper as the ammine. At Calumet and Hecla0-" With a mill tailing containing about 0.4 pct Cu as metallic copper, it has been found necessary to aerate the ammonia-ammonium carbonate leach solutions between stages to oxidize the solubilized copper. At Nicarol"-" where nickel and cobalt occur as oxides and silicates which are not soluble in ammonia, the ore is heated to decompose silicates and to selectively reduce the nickel and cobalt to metal, leaving the iron as Fe,O,, and is then leached with ammonia-ammonium carbonate solution accompanied by aeration to dissolve nickel and cobalt as ammines. In each of these leaching operations, the anion present is CO, and the metals can be precipitated from the leach solution as oxide (copper) or hydroxide and carbonate (nickel and cobalt) by boil- ing off NH, and C02 both of which are recycled to treat a subsequent ore charge. The products-—oxide, hydroxide, or carbonate—can be treated by conventional smelting, calcining, or electrolytic methods to convert them to refined metals. Thus the procedures mentioned utilize the properties of the ammines to extract copper, nickel, and cobalt from nonsulphide ores and separate them from the leach solutions. These processes have the advantage that they can be carried out in closed vessels at atmospheric pressure, that the leaching solutions are specific for the desired metals, that the metals can be recovered as relatively pure compounds by the boiling operation, and that the NH, and CO, can be recycled. Also, as the leach solutions after boiling and filtration are substantially free of metals, NH,, and CO,, they can be discarded, thus facilitating the control of the water balance in the leaching circuit. When, as is the case with Sherritt Gordon concentrates, sulphides are treated with ammonia solution in the presence of oxygen, the leach solution contains SO,--, and an entirely different set of conditions is encountered. The ammine sulphates (of nickel, for example) are more soluble than the carbonates and can be only partially decomposed by boiling. The SO, and NH, in the solutions can not be recovered by boiling. Thus, despite the more favorable leaching conditions resulting from high solubility of the ammine sulphates, the recovery of metals, NH,, and SO, from the solutions must be effected by other means. Sherritt Gordon Nickel Concentrate Treatment The Ni-Cu-Co flotation concentrate produced at Lynn Lake'" contains 12 to 16 pct Ni, 1 to 2 pct Cu, 0.2 to 0.5 pct Co, 33 to 40 pct Fe, 28 to 34 pct S, 8 to 20 pct insoluble, and less than 0.02 oz per ton precious metals. The nickel is present chiefly as pentlandite, the copper as chalcopyrite, and the iron as pyrrhotite and pyrite. Most of the cobalt is thought to be present in pentlandite, although it is known that a small amount occurs as Co-Ni-pyrite.

Jan 1, 1956

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By B. B. Sandiford

It has been known for many years that the efficiency of a water flood can be improved by lowering the water-oil mobility ratio in the system. Such a change leads to better sweep efficiency and also to more efficient oil displacement in the swept zone. Data from our laboratory water-flood tests of both small cores and long sand packs are presented which show that water mobility can be reduced and oil recovery increased by the addition of certain polymer solutions to flood water. The reduction in mobility, in many cases, is greater than would be expected from conventional viscosity measurements. These solutions, however, do not cause significant reductions in oil mobility. The over-all effect of these mobility changes is increased waterflood oil recovery. Encouraged by results of our laboratory work, we expanded our study to include pilot field tests of floods with such solutions. One such test, made in the West Cat Canyon field, Santa Barbara County, Calif., is described in detail in this paper. Three other field tests are also discussed. INTRODUCTION Oil production from most reservoirs following primary depletion and/or water flooding is often less than 50 per cent of the original oil in place. Heavy oil reservoirs seldom yield over 15 per cent of their original oil. With new reservoirs becoming harder to find, the improvement of oil recovery efficiency is one of our very important problems. We describe here some of our attempts to increase the efficiency of oil displacement by adding a water-soluble polymer, partially hydrolyzed polyacrylamide, to flood water. This technique will be termed "polymer solution flooding". The concept of using high-viscosity water to increase the efficiency of water flooding is not new. In 1944 Detling (Shell Development Co.) obtained a patent covering the use of several additives for viscous water flooding.' His objective was to improve water-oil mobility ratios by increasing the viscosity of the flood water. Other patents2-27 have been granted covering specific water-SO~LIble polymers or specific conditions of viscous water flooding. Barnes'" described his laboratory model study of the injection of a viscous water slug into a reservoir which had been partially invaded by bottom water. He concluded that, for this type of reservoir, "the cost of viscous water should not exceed a few cents per barrel for viscous water slug injection to be economically feasible" Our studies have led us to a somewhat different conclusion in a number of cases where hydrolyzed polyacrylamide solutions have been injected into reservoir models or actual reservoirs. Possible reasons for this difference are discussed in this paper. Our studies have shown that polymer solutions may lead to an increase in oil recovery over that from an ordinary water flood by (1) improving sweep efficiency, (2) improving microscopic displacement efficiency, or (3) a combination of these mechanisms. In the work of Barnes, only the benefit of improved sweep efficiency was considered. Also, our work has shown that there are marked differences in the effectiveness of different water-soluble polymers as flood water additives. Partially hydrolyzed polyacrylamide is better than many other water-soluble polymers we have tested because, even in very low concentrations, it can lead to increased oil recovery. This is an important advantage when either a dilute polymer solution is injected continuously or a relatively concentrated slug is injected followed by water. In the latter case! portions of the slug become diluted and function in the formation as very dilute solutions. As dilution takes place the effective slug size will increase which, in turn, will reduce the cost per barrel of the effective flooding medium. The reason that partially hydrolyzed polyacrylamide solutions are more efficient at low concentrations than certain other polymer solutions of equivalent viscosity (when measured in conventional viscometers) is not fully understood. We do know that the shapes and sizes of macro-molecules dissolved or suspended in liquids influence the flow properties of their solutions or suspensions. Solutions of partially hydrolyzed polyacrylamide cause greater reductions in water mobility than would be expected from conventional viscosity measurements. LABORATORY STUDIES Laboratory water floods were run in linear and radial systems with different water-soluble polymers and under varying conditions of flow. including reservoir conditions of temperature, pressure and fluid composition. Some of these runs are considered in this section. OIL DISPLACEMENT IN LINEAR MODELS In this group of runs the sweep efficiency approached 100 per cent because the linear sand packs used were as nearly uniform as possible. Results reflect primarily the micro-scopic displacement efficiencies. The laboratory models were unconsolidat-ed sand packs the lengths of which varied from about 4 in, to 40 ft. Further information on the flow models used is listed in Table 1. Using conventional procedures, water floods were run on sand packs containing either refined or crude oil at restored state. Frequently, a repeat run, similar to the first, was made as a check. Then a third run was made on the restored-state model using either polymer solution or a combination of polymer solution (slug) and water. Details of these runs are also reported in Table 1. In Figs. 1 and 2 results of two different groups of runs are shown in which the oil used was a 62-cp refined oil and the flooding medium

Jan 1, 1965

By S. M. Moos, R. E. Dugger

In reviewing available vacuum filtration equipment in this paper, several types of filters have been included which are probably not familiar to operators in the mining industry. However, it was felt that these units might be of interest in the event that an application should arise for the filtration of a product in the future that does not exist today. In addition, exposure of our industry to equipment used in other industries might have a tendency to be thought provoking and perhaps lead to the development of equipment and/or applications in our industry which do not necessarily exist at this time. Most innovations in filtration equipment have been confined to the improvement or design change of components and accessories, particularly reflecting the availability of materials of construction that have been developed. Recent developments in the application of horizontal belt filters have been innovative. The application of this unit as a substitute for or an adjunct to thickeners in a CCD circuit can certainly be innovative and perhaps provide a basis for reduction in capital and operating costs in this area. For example, mill tails are generally pumped at the highest possible density that will adequately flow. Tailings ponds and dams with their attendant design requirements are based upon this estimated water volume. Availability of a much dryer, non-flowing filter cake opens up several new options for disposal. Considerable cost savings could result in the design and planning of disposal areas for containing dryer material. No attempt has been made in this paper to provide a manual for the operation of all of the many types of equipment that are available. Rather, the paper tries to present an overview. Fundamentals of Vacuum Filtration Filtration may be defined as the separation of solids from a liquid effected by passing the liquids through a porous medium. If the filtrate is induced to flow through the medium by hydrostatic head, we refer to it as gravity filtration. If we utilize super-atmospheric pressure upstream of the medium we call it pressure filtration and if sub-atmospheric pressure is applied downstream of the medium we call it vacuum filtration. Centrifugal filtration occurs when a centrifugal force is applied across the medium. Centrifuges will not be discussed in this paper. The process goal of filtration may be the production of dry solids where the cake is the valuable product, clarified liquid

Jan 1, 1980

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators 'then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By Henry Doherty

FOR many years more money was spent in the search for and the production of gold than the gold that was produced was worth. The same thing is now true of petroleum. More money is spent for the search and. production of petroleum than the market value of the petroleum produced. The first thought concerning this statement will be that men would not embark in a business in which more money was expended than the value of the product produced. Few people realize that more money is spent in the oil business than the market value of the oil produced. This would not stop the spending if they knew it. Everybody knows that more money goes into a lottery than comes out of it, yet the instinct for gambling is so widespread and so easily excited that lotteries are forbidden by law. The hope of winning the grand prize is what lures men on. The search for and production of oil has become a more frenzied game than the search for gold ever was. THE OIL BUSINESS PAYS NOW BUT THE PUBLIC WILL PAY FOR ALL ETERNITY The public could sit back and enjoy all of this, knowing they were being supplied with petroleum products at less than their real cost, if it were not that our most valuable and least plentiful natural resource is being dissipated at an alarming rate, which is constantly increasing. Here is an industry that for many years has not been governed by natural laws. The so-called laws of individual and mass psychology play a more important role than natural physical and economic laws. Even the law of supply and demand works only in the most remote way in this industry. The oil production business as a whole is now paying the price for this folly; but the public will pay the price for all eternity. The seriousness of this matter, as an outstanding national problem, has been under consideration by many men for a long time, but nothing has been done to conserve our petroleum resources and prolong the supply, although very important steps have recently been taken to make this possible.

Jan 3, 1925