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By C. van Dijk

In Sept., 1960, a steam-drive project was started in the solution-gas drive area of the Schoonebeek field. A part(ern of three five-spots and one four-spot was selected covering an area of 65 acres. The pay in the project area has good lateral continuity and dips slightly to the northeut; it is about SO ft thick and permeability increases from 1,000 and at the bottom to approximately 10,000 md at the top. The oil originally in place was 12.6 X 10' bbl. The oil has an in situ viscosity of about 180 cp. At the start of the steam drive the cumulative primary production due to. solution-ga.7 drive amounted id 4 Percent of the oil originally in place. Reservoir pressure had dropped about 120 psi and no significant primary re-.serves remained. Some 11.3 million bbl of steam (all steam quantities are expressed in barrels of water vaporized) have been injected, resulting in production of an additional 4.1 X I0 9bl of oil, or 33 percent of the oil originally in place. This corresponds to a cumulative oil-stearn rario of 0.37 bbllbbl. It appears that the steam preferentially moves r updip while liquids are produced mainly from downdip wells observations indicate that tile steam flows through only the upper part of the formation. The lateral steam distribution in the pattern is satisfacrory since several prodriction wells hardly reacted and, hence, cori tributcd little to the oil production. Production performance and results from material balance calcutlations agree satisfactorily with the results of large-,scale laboratory experiments. On the basis of these experirmental results the .steam drive, together with a cold water follow-up. is expected to bring ultimate recovery to a value of crt leas: 50 percent of the oil originally in place. No serious production problems have been encountered. However, due to mechanical fuilure, two old prodriction wells and one injection well had to be replaced. An extension of the. steam drive in this area is under connstruction. Introduction The Schoonebeek oil field, discovered in 1943 and developed after World War 11, is situated in the eastern part of the Netherlands. The main oil reservoir in this field is the Valanginian sand. A completely sealing fault divides this reservoir into two areas (Fig. 1): the southwestern part of the sand body where primary production is ob- tained by means of a solution-gas drive, and the remain. der where edge-water drive is the production mechanism. In the greater part of the field the reservoir consists of a single, unconsolidated sand body. The net thickness ranges from 30 to 100 ft and the top is between 2,400 and 2,800 ft below sea level. Formation permeability varies from approximately 10,000 md at the top to values of the order of 1,000 md at the bottom, and porosity is about 30 percent. The reservoir contains a paraffinic oil of 25" API gravity with an in situ viscosity of 160 to 180 cp. Initial oil saturation was high (85 to 90 percent). The relatively large quantity of oil in place (more than 10' bbl), and the low ultimate primary recoveries expected from this field — approximately 15 percent stock-tank oil initially in place (STOIIP) for the water-drive area and 5 percent STOIIP for the solution-gas drive area — clearly indicate ample scope for secondary recovery. Because ies-ervoir and crude characteristics made this field suitable for thermal secondary recovery, a hot-water drive project was started in the water-drive area about 10 years ago. A few years later a steam drive and an in situ combustion project were started in the solution-gas drive area. This paper deals with the performance of the steam-drive project, which was started in Sept., 1960, and which is still in operation. Design of Steam-Drive Project, An experimental investigation of the steam-drive process carried out by schenk in 19561 indicated that under schoonebeek conditions steam injection could be an attractive secondary recovery method. the findings and encouraging results of a pilot test in the Mene Grande field in venezuela,i led to the design of a steam-drive project in the schoonebeek field, Pruject Site and Pattern In 1958 the reservoir pressure in the solution-gas drive area had decreased to about 120 psi, and oil production rates of wells in this area had dropped to 7 to 10 B/D. The cumulative primary production was about 4 percent STOIIP, leaving an oil saturation of approximately 85 percent. In view of the large amount of oil left behind in the reservoir, the solution-gas drive area was selected for the planned steam-drive project. The area in the vicinity of Well S1 3 (Fig. 2) was considered to be suitable since it is at least partly isolated from the rest of the field by faults and the sand is relatively thick (about 80 ft).

Jan 1, 1969

By A. M. Gaudin

THE study that is presented here was undertaken in order to condense information concerning comminution, and covering a great variety of conditions, into one or several rules which would be of use in the development of a systematic theory as well as in many directly practical ways. As the result of this work, the following conclusions appear justified 1. Rocks may be classified, from the point of view of comminution, into two general classes which are (a) structurally homogeneous, and (b) structurally heterogenous. Structurally homogeneous rocks are those in which fracture takes place through grains and grain boundaries alike; heterogeneous rocks are those in which fracture passes in preference through grain boundaries. 2. If a sized product composed of structurally homogeneous rock grains is crushed, a product results in which the relation between the percentage weight of grains of various sizes and these sizes themselves follows a definite law. This is not true of structurally heterogeneous rocks. 3. Ball milling with structurally homogeneous rocks, and under certain conditions, presents exceptions to this rule. 4. In ball milling with structurally homogeneous rocks, there exists a critical ratio of size of feed to size of balls, above which the machine operates essentially by surface wear, and below which it operates essentially by breaking across the body of the particle. 5. In ball milling, with structurally homogeneous rocks, and when the size of feed grains exceeds the critical size, the particles worn off are of a, substantially definite size which depends upon the ball size 6. In the case of a typical heterogeneous rock, such as Manhattan schist, particles are crushed in such a way that there is a greater proportion of grains of the size that is the average grain-size of the rock than there would be in that range of size with a structurally homogeneous rock. This has been found to be true with-all the crushers tested. 7. Different methods of crushing produce grains of different shapes.

Jan 2, 1926

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967

By D. W. Frommer

Processing nonmagnetic taconites by selective flocculation-desliming and flotation requires large volumes of water. If impounded without treatment, these off-process waters require excessively large areas for containment. To discharge the waste water into natural waterways would contribute to stream pollution and likely would not be permitted. In U.S. Bureau of Mines experiments conducted in the Twin Cities Metallurgy Research Center's 900-lb per hr pilot plant, approximately 85% of water requirements for the flotation-based treatment of a Michigan nonmagnetic taconite were met by reclaimed water. Water reclamation of the off-process streams from flotation was accomplished by controlled additions of lime, sodium carbonate, and a synthetic flocculant to reduce turbidities to 51000 ppm equivalent SiO*, while maintaining a Ca(II) content of =16 ppm in the finished effluent. Flotation concentrates of good quality were obtained using the reclaimed water. The cost of chemicals used in water reclamation was approximately equal to the savings in flotation reagents attributed to recycling of the water. Water quality is perhaps as important to flotation as are the reagents used. The character of water is extremely variable, depending on whether the source is a well, lake, or stream, upon the season and temperature, upon prior use, and upon the character of the watershed. All of these factors influence the water hardness and the quantity of other dissolved inorganic salts, turbidity, dissolved and suspended organic matter, dissolved gases, and pH. Frequently, the differences in water quality can measurably influence flotation selectivity, often to the point of spelling success or failure. Water hardness is particularly troublesome in flotation systems employing fatty acids, but other unrecognized constituents may also contribute to peculiarities in flotation behavior. Furthermore, a given water source may be entirely satisfactory in one flotation system, but entirely inappropriate in another. In recent years, society has given more attention than formerly to water use, even in areas where water is plentiful. However, both the demands of a growing population, with increased per capita needs, and also those of industry must be met. As a result, riparian rights must be negotiated with the appropriate government agency or agencies so that consumption of water is often allocated or otherwise controlled. Furthermore, the disposal of off-process industrial and domestic water is coming under the increasing scrutiny of these same governmental units. In these respects, the mineral industry is no exception, so that conservation, water reclamation, and reuse may be expected to assume increasing importance. In 1932, it was stated that, "water reclamation is generally more expensive than the economy in water and reagents resulting from its use. It is employed only if it is urgent to save water."' The economic aspects of this statement may still be true, but the unrestricted use of water is becoming less and less an option of the user. The purpose of this paper is to discuss an investigation conducted by the U.S. Bureau of Mines (USBM), in which water reclamation and treatment were undertaken to develop procedures for, and to assess the effects of, water reuse on the flotation treatment of nonmagnetic taconites. This investigation is a logical extension of previous work described by the author and associates at the Twin Cities Metallurgy Research Center employing selective flocculation-desliming and anionic flotation of silica from low-grade, nonmagnetic iron ores2,8 The requirements for the selective flocculation-de-sliming and the anionic flotation of silica processes determined the direction of the investigation. Previous studies had indicated that pH levels of about 11.0 and 11.8 were required for selective flocculation and flota-tlon, respectively. The calcium content of the water was believed to be of importance in both of these operations, and since Minneapolis tap water with a Ca(I1) content of about 16 ppm had been successfully used, an attempt was made to reclaim the process water at an equal level of dissolved calcium. Additionally, the objective was to nullify or effectively limit the effects of dispersants and fatty acid residuals from prior stages of processing. Last but not least, the system of water treatment had to have the capability of reducing turbidities to workable levels. With about half of the effluent being derived from the selective flocculation-desliming step and carrying about 25,000 ppm of highly dispersed, suspended fines, this last objective appeared formidable at the outset. Procedures for water reclamation were derived, in part, from well-known mineral dressing practices, from past observations and investigations, and from concepts contained in various pertinent publications on water treatment."c These procedures involved: 1) flocculation with lime and poly electrolyte-type flocculants, 2) lime-soda-ash softening, 3) chemical precipitation, and 4) mineral surface adsorption. Control was exercised at various stages of water reclamation by frequent measurements of Ca(11), pH, and turbidity.

Jan 1, 1971

By R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13. per cent, of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 258, Special 178 and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings.

Jan 1, 1927

By J. Clair, H. Mirabel

The determination of the temperature and electrical potential distributicms in the cathodes of aluminum electrolytic cells is difficult. The reascms come from the various nature and the intricate three-dimensional geometry of the materials; besides thermal and electrical phenomena react upon each other. A method of calculation using a computer program applied to a mathematical model, figuring the cathode, is developed. Both of the thermal and electrical phenomena are simultaneously considered. Temperature and electrical potential distributions are finally obtained by successive iterations. Results are compared with measurements on industrial cells. Theoretical and practical applications of these studies are given. Up to the present time the study of the distribution of the temperatures and electric potentials in the electrodes, anode and cathode, of the electrolytic cells used for the production of aluminum was limited to one of the two aspects of the phenomena because of lack of a simultaneous method of calculation. For example, the anode or cathode drop was studied assuming that the temperatures in the iron and carbon are known, a method that obviously is very approximate since iron resistivity, in particular, greatly varies with temperature, which in turn depends on current density. Consequently we tried to find a method of calculation simultaneously taking into account both thermal and electrical phenomena. We proceeded to the study of the cathodes as an initial approach to the problem. Although the cathode and surrounding materials may have varied forms and particularly very heterogeneous characteristics, their structures are simpler than that of the Sijderberg anode and boundary conditions are more easily represented than in the case of anodes even though they are prebaked. The study was in two parts: a) development of a model schematizing the true geometry of a cathode and defining the thermal and electrical boundary conditions, and b) working out a method of calculation of the temperatures and potentials by means of an electronic computer. To facilitate solution of the problem, a model was used initially much simplified in comparison with an actual cathode. This model permitted development of the method of calculation. In a second phase, this model was adjusted to the study of actual cathodes and applied to different types of cells: low- or high-intensity cells, cells set up at ground level or above ground level, cells with cathodes more or less heat-insulated. Simultaneously measurements were made with cells equipped with cathodes of the types studied to compare the values resulting from calculation. The initial model was also used for general studies, in particular for studying the effects of current density in the carbon and iron. The results were confirmed or made precise by the model of the true cathodes. This report successively describes: a) the manner in which the model representing a cathode was worked out, with the simplifications and/or the hypotheses used, b) the method of solution of the problem by means of the electronic computer, and c) an example, stating the extent to which the results obtained may be realistic. Further the possibilities offered by such a study are examined. 1) CATHODE REPRESENTATION The purpose of this phase is to represent the cathode in the form of a so-called "mathematical model", that is with a simplified geometrical configuration, in order to meet the subsequent calculation requirements, while keeping to the true facts as closely as possible. This model further includes the thermal and electric conductivities with regard to temperature for the varied materials composing the cathode, as well as the thermal and electrical conditions at the model boundaries. 1.1) Guiding Principles. For calculating the temperatures and potentials the model is divided by trior-thogonal planes into a network of small elementary parallelepipeds. At the summit of these parallelepipeds' so-called mesh points, the temperatures and potentials are computed. The number of mesh points is of course limited by the capabilities of the computer, since 1) the number of equations to be solved depends on the number of mesh points selected, and 2) the amount of time spent by the computer considerably increases with increasing this number. These conditions call for the following requirements as concerns the model: a) Dimensional requirements: the calculation will be all the more accurate as the network is more closely meshed. Since the number of mesh points is limited in practice, it is necessary to restrict the dimensions of the model. b) Geometrical requirements: so as to make things easier in working out the network, the model must be given a simple geometry. In particular, it will be convenient to have the cathode so constituted that the surfaces limiting the cathode and the surfaces within the cathodes separating the different materials consist of triorthogonal planes. 1.2) Schematization of the Cathodes. After the tech-

Jan 1, 1968

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By G. F. Comstock

In the literature of metallography there is a large amount of material describing the various non-metallic inclusions found in iron and steel, and the appearance of sulfides, silicates, oxides, or alumina in steel under the microscope is fairly well known. The inclusions found in non-ferrous metals are, however, not so well known, at least judging from published writings, and the author has been interested in examining small castings of copper, brass, or bronze with certain inclusions purposely mixed with the metal, to see what was the characteristic appearance of each kind of inclusion, and if they could be readily distinguished from one another. The method employed in most cases consisted in overheating and oxidizing a small charge of copper, then cooling it somewhat, and adding a suitable amount of the element whose oxide it was desired to observe. This element was stirred in well and given time to react with the oxygen in the copper, then the melt was poured in a sand mold in the form of a cylinder about 21/2 in. (63 mm.) in each dimension, with a sprue about 11/2 in. (38 mm.) in diameter and 3 in. (76 mm.) high on top of the cylinder, the sprue forming the only riser. Samples for examination were cut sometimes from the center of the casting, and sometimes from the sprue or riser. A few of these samples were cast in chill molds. The appearance of sulfides was studied in an alloy containing 10 per cent, each of tin and lead, with which a flux of plaster of Paris was used. The appearance of foundry sand was studied in several alloys, one of them having sand stirred into the metal intentionally, and others having cut into the molds badly when poured, so that the castings were spoiled by included sand. As all this work was done on alloys having copper as the chief ingredient, the natural starting point was copper oxide, the appearance of which in a micro-section is well known. Cuprous oxide is soluble in molten copper, but separates out in freezing and forms a eutectic containing 3.5 per cent. Cu20, or 0.39 per cent. oxygen. If there is less

Jan 1, 1919

By S. D. Strauss

The marketing of nonferrous metals and of the ores and concentrates from which these metals are recovered is a fascinating trade, international in character, sensitive to every change in the economic tide, and complex in its organization. Each individual metal has its own marketing mechanism; no two are exactly alike. The differences sometimes are a matter of tradition rather than of necessity, but usually they have developed because of the very nature of the problems of producing or consuming the individual metal. This description, because of limitations of space, can do no more than indicate the major aspects of the trade and touch lightly on the marketing structure of each metal. The dictionary states that a market is a "meeting of people for selling and buying." In the case of nonferrous metals this meeting may occur on a half-dozen different occasions between the time the ore has been first mined and the time the refined metal is available for use by industry; or it may not occur at all until after the metal itself has been rolled, drawn, stamped, cast, or forged into a useful semifabricated shape. To illustrate: A Chilean miner may sell his small ore production to a custom mill, which produces concentrates that are sold to an ore dealer, who finances shipments of the concentrate to a custom smelter, which buys them for conversion into blister, to be subsequently refined into electrolytic copper (sometimes by a refinery having no corporate ties with the custom smelter) and sold. Conversely, aluminum production is mostly by integrated concerns that mine bauxite, convert it to alumina, smelt that to produce aluminum, and then fabricate that into semifinished or even finished products before title to the material changes hands for the first time. Some nonferrous ores are not converted into metal at all but are sold by the miners or dealers directly to the ultimate consumers. A good example would be chrome ores used by the chemical industry. And of course a substantial part of the commerce in nonferrous metals is in scrap, which is the reconversion into useful form of metals that have long since been mined and smelted. Thus, one-third of all the lead used in the United

Jan 1, 1964

By David Sinclair, Philip B. Bucky

The dimensions and shapes of mine structures may at present be determined by (1) field experience, (2) structural calculations, and (3) barodynamic tests. § None of these, however, provide information as to the stresses, their direction and distribution in a mine structure. For the design of pillars, the placing of openings relative to working places such as gangways, haulage levels, etc., this information is desirable. Photoelastic methods provide this and, while relatively new, their application in all engineering fields is assuming increasing importance. This paper, therefore, will present the method with a few applications to mining, and with sufficient reference for further study by the reader. PART I The Photoelastic Method The photoelastic method of stress measurement determines the stress distribution in a two-dimensional model by optical means. It makes use of the fact that when a piece of isotropic transparent material, such as glass, celluloid, or Bakelite, is stressed and viewed in polarized** light a picture is seen which indicates by its color bands of light, or fringes, the magnitude of the stresses, their direction and their distribution. General Explanation The stress at any point 0 in a structure (Fig. I), may be resolved into two components, P and Q, each a pure tension or compression, at right angles to each other, called principal stresses.&apos; To fully identify the stress, the values of P and Q and their directions or angle F must be known.

Jan 1, 1940

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol&apos;kenshtein&apos;s effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS&apos; attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By A. C. Heath, E. H. Dix

THE importance of aluminum-silicon alloys in the light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and like silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminum and aluminum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. PART I.-ALUMINUM-SILICON ALLOYS The early work on this system was largely confined to determining the general form of the diagram and in this respect the results are in good agreement. Briefly, aluminum and silicon form a simple eutectiferous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Fraenkel1 (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solution. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility does not appear

Jan 1, 1928

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells&apos; effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer&apos;s Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding&apos; showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,&apos; the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By Harold Earle Cook

The purpose of this paper is to state briefly the inspection requirements of the Bureau of Ordnance, the specifications governing the inspection, and the physical and chemical properties of the steel used in the construction of ordnance for our Navy. It would be of interest to evoke discussion on points in these specifications which do not tend to insure the production of the very best material for the purpose intended. In other words, what requirements of our specifications are useless and also in what manner are our specifications deficient? It might be well at the start to answer the first criticism of this paper which will probably be made, and that is that the title does not agree with the subject matter. Considering metallographic work as covering only the macroscopic and microscopic examination of metals, this paper will have gone beyond the subject; but it is believed that a broader definition of metallography is that it is the study of the relation of the internal structure of metals and alloys to their composition and to their physical and other properties. The internal structure of steel is dependent on its physical and its chemical properties. These physical properties are dependent on the chemical composition and the mechanical and thermal treatment of the steel. So it seems that this subtitle would not be entirely necessary and that the title " Metallography of Steel for Ordnance Purposes" would cover a study, not only of what we can learn of macroscopic and microscopic examination, but broadly of the whole subject of the specifications, the fulfillment of the requirements of which produce the structural conditions revealed by macroscopic and microscopic examination. I will refer but briefly at the beginning to the microscope and its uses in our inspection. It is only very recently that the Bureau of Ordnancc has furnished certain of its inspection offices with a portable Tassin outfit for the microscopic examination of steel. Since that

Jan 1, 1916

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe&apos;s laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe&apos;s death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.&apos; Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.&apos; They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE studies of the mechanism of precipitation and of the resulting property changes in aluminum-silver alloys1-3 have presented some new concepts of the aging reaction-concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.1,4 These platelets grow in lateral dimensions and in thickness with aging time until they are thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstätten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuous precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 EXPERIMENTAL PROCEDURE The alloys were made using 99.97 per cent Al or distilled magnesium, with

Jan 1, 1943

By E. H. Jr. Dix

DURING an investigation of high-strength manganese bronze by the Engineering Division of the Air Service, at McCook Field, Dayton, Ohio, particles of a "blue constituent" were noted in the microstructure of most of the bronzes examined. The constitution of the simple copper-zinc base alloy is still a matter of dispute in spite of the fact that the copper-zinc series is one of the oldest industrially important groups of alloys, and has received the early consideration of scientific research. The diagram, according to the most recent work,1 is shown in Fig. 1. The disputed questions involve the termination of the beta field and the line at 470° C. The earliest experimenter, Roberts-Austin, detected an arrest in some of his cooling curves at approximately this temperature and ascribed them to the formation of a eutectic; it has since been proved that there are no eutectics in this series. Shepherd2 was unable to detect any thermal arrests at this temperature; his diagram was essentially as shown in Fig. 1, except that the line at 470° C. was omitted and the beta phase carried down to normal temperatures. Later, Carpenter and Edwards,3 by a very painstaking research, definitely established the authenticity of the line but attributed it to the breakdown of the beta constituent into a eutectoid of alpha and gamma. Microscopic evidence of the formation of the eutectoid is doubtful and it seems more likely to be due to an allotropic change in the beta constituent as shown by Fig. 1. At least for practical purposes, it is more convenient to think of the structure of a 60-40 brass as a mixture of alpha and beta prime crystals rather than alpha plus an unresolvable eutectoid of "apparent beta" as it has often been called.

Jan 5, 1922

By Edward C. Jeffrey

The use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years—the middle of the 17th to the middle of the 18th century—there .was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate. Two of my colleagues, who are taking part in this discussion, will describe the valuable results that have been reached by studying coal by the methods of the mineralogist. Doctor White and Doctor Thiessen have studied the structure of coal as determined from thin sections that

Jan 1, 1925

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith&apos; while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith&apos;s experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours&apos; exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960