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By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators1,2,3 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By C. E. Sims, H. M. Banta, S. L. Hoyt

Over the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking— specifically underbead cracking, or "hard cracks," or parent-metal cracks-—is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.' The tests described are made under restraint to facilitate cracking and arc so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when are-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institutc on two projects, one

Jan 1, 1945

By E. L. Tucker

IN THE metallurgy of precious metals, it has been standard practice for years to use cyanogen compounds, so it was but natural that early investigators in the field of flotation should consider these compounds as possible flotation reagents. In Australian Patent 9508, of 1913, alkali cyanides were described as suitable reagents for the separation of heavy sulfide minerals, the reagents being employed either in an alka-line or neutral circuit. In U. S. Patent 1236501, of 1917, to John M. Tibbet, the use of cyanide in conjunction with soda ash or lime is described. One of the claims of this patent reads, "An improvement in the cyanide process for the treatment of ores comprising, mixing the ore with cyanide solution and oil and alkali: emulsifying the oil in the presence of the ore, the alkali and the cyanide solution, floating a portion of the values in the pulp by producing gas bubbles in the mixture-and removing the values floated." More recently, Sheridan and Griswold, in U. S. Patents 1421585 and 1427235, describe a somewhat similar process and have, successfully introduced it in. the mill of the Timber Butte Milling Co. U. S. Patent 1429544, of 1922, to Stevens, describes the use of double cyanides of copper, zinc, and lead. The success of cyanide as a reagent in the differential flotation of lead and zinc sulfides in highly complex ores is proof that these patents have a solid foundation.. Although the technique of their application to particular ores has been worked out in many cases, no one, so far as is known, has attempted to describe the nature of the action of the cyanide or to determine the ideal conditions for its, application. It was the purpose of the present investigation to gather information on these points. Naturally this would have been an exceedingly ambitious.

Jan 8, 1925

Jan 1, 1951

By H. N. Thomson

GENERAL. THE Tooele plant of the International Smelting & Refining Co. is situated at the mouth of Pine canyon, Tooele county, Utah. It is connected with the main line of the San Pedro, Los Angeles & Salt Lake railroad by the Tooele Valley railway, and is about 7 miles from Tooele Junction. Fig. 1 is a general view of the plant. FIG. 1.-TOOELE PLANT OF THE INTERNATIONAL SMELTING & REFINING Co. The copper plant has been in operation since July, 1910, and the first blast furnace at the lead plant was blown in on Feb. 29, 1912. The location of the plant was selected on sloping ground with the idea of using gravity to the fullest extent and thus keeping labor at a minimum. Practically the entire plant is constructed of steel, reinforced concrete, and brick. Bingham ores, both lead and copper, are received over the Utah Consolidated Aerial Tramway. The tram buckets, each containing

Jan 7, 1913

Mining and Metallurgy of Lead and Zinc, AIME Vol. 121, edited by Dr. C. R. Hayward in 1936, remains a document of importance today even though 34 years have passed in the meantime. Since nothing in this world seems to be permanent, however, and progress brings new and better ways to do things, a two-volume set has just been published to bring the state of the art of 1936 up to date. This two-volume set, Mining and Concentrating of Lead and Zinc and Extractive Metallurgy of Lead and zinc, incorporates the papers to be presented during the Proceedings of the 1970 World Symposium on the Mining and Metallurgy of Lead and Zinc. The Symposium is being held October 20-24, 1970, in St. Louis, a site near to the famous Lead Belt of southeast Missouri. Some eighty papers are bound in these two volumes covering exploration, geology, mining, concentrating, roasting, smelting, electrolytic processing, residue fuming, refining, etc. All of this is laced with data on tonnages, processes, assays and efficiencies obtained, and the man-hours and equipment needed to achieve these performances.

Jan 1, 1970

By A. W. McReynolds

One characteristic of plastic deformation which distinguishes it from elastic strain is the essential inhomo-geneity of plastic strains. Elastic strain varies continuously through a material, and average relative displacements of initially adjacent atoms are only small fractions of their initial spacing, (strains of the order of 0.01 or less). On the other hand, plastic flow corresponds to the appearance of discontinuities in strain of the lattice, such as dislocations or slip bands, where local strain, on an atomic scale, is several orders of magnitude higher. These discontinuities are visible on a microscopic scale as the familiar slip lines (Fig 1). In spite of this obvious microscopic inhomogeneity, however, macroscopic measurements almost invariably show a smooth curve of stress vs. strain (Fig 2b) even if measurements of linear strains be made to an accuracy of one part in 107. This macroscopic homogeneity of strain indicates that the discontinuities in strain on slip planes occur in increments too small or too slow to be recorded individually, and further that they occur sufficiently independent of one another so that the small increments add at random to a smooth stress-strain curve. The present paper describes observations of plastic strain in aluminum of commercial purity and in high purity Al-Cu alloys, where there exists a strong coupling between slip in various regions of the specimen such that once initiated it spreads rapidly through a large volume. The total effect is that of relatively large, rapid, and regularly spaced steps of strain followed by periods of only elastic strain. Fig 2a illustrates the type of "stair-step" stress-strain curve which results. The properties of this cooperative slip phenomenon will be described further in the section on results: in par- ticular it will be shown that each step corresponds to the propagation of a wave of plastic deformation through the specimen. Some interpretations of the mechanism by which it occurs will be made in the following section. Although the type of plastic wave phenomena to be described has not previously been reported, there are numerous cases of related effects in the plastic yielding of metals: YIELD POINT PHENOMENA The most familiar of such effects is the "yield point" observed in low carbon steels, brass, duralurninum, and the like. It consists in the sudden termination of the elastic portion of the stress-strain curve by a large plastic strain. Since the usual tensile machine is such that yielding of the specimen relieves the load, the resulting curve is as shown in Fig 3. As the strain continues, deformation occurs at a lower stress for some time, then follows a rising curve, but with no further sudden yielding. This effect has been observed in brass by Sachs and Shojil and later by many others. Edwards, Phillips and Jones2 made extensive studies of the effect in steel, and of the role of various alloying elements. Although there seems to be fairly clear evidence that the yield point is caused by a hardening of the material by precipitation of impurities, no satisfactory explanation for the sudden yielding has been given. Winlock and Leiter3 have shown that the strain. level of the upper yield point depends strongly on the rate of loading, the yield point increasing by almost a fac- tor of two as the strain rate goes from 0.002 in. per in. per min. to 4.4 in. per in. per min. This effect would seem to imply an incubation period before yielding is initiated at a certain stress. On the other hand, by going to very slow loading rates, Edwards, Phillips and Jones2 showed that the yield point does not become lower and eventually disappear as might be expected, but, on the contrary, begins to rise at loading rates below about 25 Ib per in. per min. becoming much higher than at rapid loading rates. STRAIN AGING If, instead of continuing straining of a specimen after occurrence of a yield point, the load is removed and the specimen aged, resumption of the test results in occurrence of another yield point as shown by the dotted curve of Fig 3. The new yield stress is generally higher than the previous maximum applied stress. This hardening of the material by straining and subsequent aging is undoubtedly related to quench age-hardening resulting from the aging of a specimen quenched from high temperature. Since neither effect is observed in pure metals, it is generally accepted that quench-aging in all cases is the result of hardening by precipitation of a supersaturated alloying element, and that strain-aging is probably a similar precipitation, accelerated by disruptions of the lattice by previous strain. Pfeil4 has shown that strain-aging does not occur in iron from which all of the carbon has been removed, but that only a very small carbon content, around 0.003 pct, is necessary to cause strain-aging. In accord with this observation is recent work by Dijkstra5 in this laboratory showing that the solubility limit of carbon in iron is extremely low, less than 0.001 pct at 400°C. Edwards, Phillips and Jones2 have shown that the strain-aging effect is also removed by the addition of small quantities of elements such as Mo, Mn, Ti, and the like, which readily form carbides. Their results demonstrate the

Jan 1, 1950

By Frank Corwin

It is the purpose of this article to give a brief account. of the experimental work and to show how the increase in efficiency was brought about. Part of the experimental work described in this paper was carried out by the writers, while in the employ of the Anaconda Copper Mining Co., under the direction of M. W. Krejci, Metallurgist, and Arthur Crowfoot, Chief Sampler. Complete records of all of the MacDougall testing work have been placed at our disposal through the courtesy of A. E. Wheeler, Superintendent. II. BRIEF HISTORY OF PRESENT MACDOUGALL PLANT. The first change from the Brueckner cylinders used for roasting concentrates at Great Falls was the construction of a MacDougall roaster of the Herreshoff type. This furnace was first started on June 15, 1898. It bad eight hearths, was lined with fire brick, and had an air-cooled central shaft, but no provision was made for cooling the rabble arms. It was operated for a while, and accomplished the work of roasting, but ran so hot that the rabble arms became twisted and distorted out of shape. To prevent the furnace from becoming too hot a device was then installed to draw the heated gases away from the hearths. This consisted of a pipe connected to alternate hearths of the MacDougall furnace and also connected to the flue. It was equipped with dampers, 'so that the hot gases could be drawn away from any one of the alternate hearths directly into the flue.

Jan 7, 1913

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By J. E. Korski

Quebec Cartier Mining Co. operates a low-grade iron ore deposit at Lac Jeannine, Que., which is located at the extreme southwestern end of the Quebec-Labrador Trough (Fig. 1). The facilities there include one of the world's largest concentrators, a hydroelectric plant of 60,000 hp, and the modern town of Gagnon. A 191-mile railway connects the mine to the seaport situated at Port Cartier on the St. Lawrence River. The harbor in Port Cartier can accommodate both lake and large ocean- going vessels and is also the site of a major grain terminal. The concentrator in Lac Jeannine is designed to produce some 8 million tpy (tons per year) of specular hematite concentrate, containing 66% Fe, from approximately 20 million tons of crude ore. An annual stripping program of 5 to 8 million cu yd of waste rock uncovers the required ore. Approximately 100,000 tons of ore and waste are removed daily on a year-round, 24-hr-per-day basis. The open pit covers an area with maximum dimensions of 8,000 x 2,600 ft (Fig. 2). Present mining plans call for an ultimate depth of approximately 1,000 ft below original ground level. The rocks in the pit area are typical of this portion of the Grenville geological province. They consist largely of marble, quartz rock, pegmatite, iron formation, and stratigraphically older gneisses. The iron-ore formation consists of medium to coarse-grained specular hematite in a quartz host rock. The formation occurs locally in a plunging, anticlinal form. The topography in the vicinity of the mine is rolling, with maximum variations in elevation of about 400 ft. The hills are thickly wooded with birch, black spruce, and some tamarack. Lakes and muskeg areas are plentiful. Precipitation and temperature records have been kept since 1959. The annual rainfall has ranged between a low of 23 in. and a high of 42 in.

Jan 1, 1969

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By H. M. St. John

MAINTAINING a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in-widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in. any investigation of the various factors that influence the structure and other properties of the casting.

Jan 1, 1930

By Zay Jeffries

Each generation accepts the developments of the preceding generations without full appreciation of the difficulties that had to be overcome or of the effect of any given development on society. Today, the production of pig iron is the yardstick with which general industrial health and progress are measured. So natural and logical does this seem to us, that it is difficult to picture conditions prior to the fourteenth century when pig iron was unknown. Not only was pig iron unknown but iron or steel could not be melted and poured into castings; all iron and steel articles were forged from sponge iron. All castings, as well as many worked articles, were made of non-ferrous metals or alloys. In many parts of the world, over long periods of time, not only was the annual exchange value of non-ferrous metals greater than that of iron and steel, but their combined tonnage was greater. At present, the value of the pig iron produced in a year is of the same order of magnitude as that of all non-ferrous metals combined; the tonnage of pig iron is, however, about twenty times that of all non-ferrous metals combined. Owing to lack of records, we will probably never know the relative importance of the various metals at all periods in historic times. A certain conclusion is that the iron and steel industry, since the discovery of pig iron and the cheap methods of converting it into steel, has grown at a much more rapid rate than the non-ferrous metal industries. Notwithstanding their fundamental fitness for man's needs, iron and steel owe their importance in no small degree to the low cost of production. The low cost was a result of increased knowledge of the production appliances and of the metallurgical processes. This increased knowledge is the key to our modern industrial civilization. It will remain for future generations to determine whether there is now going on a gradual change toward greater importance of the non-ferrous metals, as compared to iron and steel. The world's pig iron production in 1920 was slightly more than twice what it was in 1890, whereas the non-ferrous metals production in 1920 was about two and one-half times that in 1890. Every non-ferrous metal industry has shown marked growth during the last thirty years. During this period, the production of cop-

Jan 1, 1924

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By M. A. Jones

Performance of a pilot flood in eastern Kansas indicates improved recovery and accelerated production resulting from mobility ratio control obtained by adding a high moleculur weight polymer to injected water. Ultimate pilot flood recovery of the 75-cp reservoir oil is anticipated to he 350 bbllacre-ft during the six-year flood life. Cumulative recovery to date totals 242 bbl/acre-ft after 30 months of injection. Reservoir parameters and flood performance are disc~rssed in detail to provide a case history relating to the feasibility of polymer flooding. INTRODUCTION The Vernon Polymer flood of the Brazos Oil & Gas Co., located in Sec. 2, 24 S., 16 E., Woodson County, Kans., was begun in late Oct., 1963. Injection of a 500 ppm solution of Pusher* polymer was initiated in a 15-acre pilot to determine feasibility of improving oil recovery by mobility ratio control. Performance to date and the anticipated recovery of 115,000 bbl from the 329 acre-ft pilot indicate efficient displacement of the viscous reservoir oil. Dependence of flood recovery on the displacing fluid-displaced oil mobility ratio has long been recognized. Displacement efficiency of the reservoir oil decreases with increasing mobility ratio. Therefore, economic reduction of this parameter is an attractive approach to improving oil recovery. particularly from viscous oil reservoirs where mobility ratios are often quite high. Waterflood mobility ratios can be controlled by dilute solutions of certain polymers'; which provide a displacing fluid with considerably reduced mobility. Reservoir parameters and flood performance are emphasized in this paper to provide data relating to polymer flood applicability. THEORY The polymer used in the Vernon pilot exhibits the property of unusually high resistance to flow through porous media.'.' A small concentration in injected water effects a mobility reduction considerably beyond that predicted from increases in bulk viscosity as measured in a capillary or rotating cup viscosimeter. Water mobility in the subject flood is reduced by a factor of 7.55 with the addition of 500 ppm Pusher chemical to injected water while the bulk viscosity is increased from 1.03 to only 1.40 cp at 75F. The exact flow mechanism causing resistance to flow has not been established; however, it is observed only in tortuous flow systems and appears to be influenced by brine properties, rock properties and oil saturation. Consequently, mobility reduction is estimated from flow studies for a given sample of reservoir rock and is expressed in terms of a "resistance factor".' This parameter is defined as the ratio of brine mobility to polymer solution mobility measured at residual oil saturation: RF= ?m/?p= (km/µm)/(kp/µp)M.......(1) where RF = resistance factor (dimensionless) k*. and A, = mobility of water and polymer solution, respectively k,,, and k,, = water and polymer permeability, respectively (darcies) µie and µp = viscosity of water and polymer, respectively (poise). Eq. 1 is similar to the expression commonly used to relate the relative mobility of the water bank at residual oil saturation to oil-bank mobility at irreducible water saturation: where M =mobility ratio of water to oil (dimension-less) A, = mobility of oil k, = permeability to oil (darcies) )i* = oil viscosity (poise). From Eqs. 1 and 2 it is apparent that the polymer-solution-to-oil-mobility ratio can be approximated by dividing the brine-to-oil ratio by the resistance factor RF: Mpn=M10/RF...........(3) where M,-, = mobility ratio of polymer solution to oil (dimensionless). This simplified presentation assumes no dilution of the polymer solution by connate water. Also, the presence of a connate water bank separating the polymer solution from the displaced oil is not considered. Displacement of oil by waterflooding is increasingly dominated by viscous forces as the viscosity of the oil displaced increases. When the oil mobility is less than that of the injected water, the oil-water interface is not a piston-like front.3,' Instead, instabilities occur at the flood front in the form of viscous fingers which tend to penetrate the less mobile oil bank. The magnitude of these protrusions, or the degree of channeling, increases

Jan 1, 1967

By Shawn T. Sorrell, Carl Hrovatic

Original by Carl Hrovatic and Shawn T. Sorrell Revised by Carl Hrovatic Land is a precious resource and should be treated as such by all members of our society. The soil covering this earth is only a very thin outer layer, varying in thickness from a few inches to a few feet and covering the rocks and minerals lying beneath the surface. The wise use of this valuable commodity is the responsibility of everyone. Many everyday activities disturb the earth's surface. Examples are highway construction, housing and commercial developments, agriculture, and various types of mining. This chapter discusses the relationships of the environment to land as it applies to surface operations in the coal industry. Mining by surface methods disturbs, for a brief period of time, thousands of acres of land annually. In addition, refuse piles, slurry ponds, abandoned mine structures, unprotected mine openings, and unsightly cleaning plants can also adversely affect land unless properly handled. ACTIVE SURFACE MINING OPERATIONS Mining by surface methods includes rock quarries; sand and gravel pits; huge open pits to extract iron, copper, phosphate, and other ores; and coal mining. Production of coal by surface methods is now approaching 408.2 Mt/a (450 million stpy), amounting to almost 60% of the total coal output. Surface coal mining can be classified into the following five broad categories : Open-pit mining is practiced where coalbeds are extremely thick, as in some western states, or where coalbeds are sharply pitching, as in the anthracite region of the eastern United States. A typical open-pit mine, with coalbeds of 3.05 to 30.5 m (10 to 100 ft) or more thickness and a

Jan 1, 1981

By Robert Keeney

Before the outbreak of the war in 1914, the only electric-furnace smelting plant operating on a commercial basis west of the Mississippi River was an electric pig-iron plant in California; rare metal ores were not smelted, concentrates of molybdenum, tungsten, uranium, and vanadium ores being shipped east for reduction. Practically no- chrome ore was being mined, and only comparatively small amounts of manganese ore. Today there are two electric smelting plants in California, one in Washington, one in Iowa, and four in Colorado; two plants are under construction in California, and one in Montana. Ores of manganese, chromium, molybdenum and tungsten are now smelted in the West, and although uranium and vanadium concentrates are still shipped to the East, they will probably be treated in western plants in a short time. The four electric-furnace plants in Colorado are listed in Table 1. TABLE 1.-Electric Smelting Plants in Colorado Capacity, Company, Location Kilowatts Products . Tungsten Products Co Boulder 800 Ferrotungsten, ferromolybdentun. Boulder Tungsten Production Co. . Boulder 400 Ferrotungsten. Ferro Alloy Co Utah Junction 1200 Ferrochrome, ferrotung-sten. Iron Mountain Alloy Co Utah Junction 3000 Ferromanganese. Power for all of these plants is supplied by the Colorado Power Co.

Jan 8, 1918

By J. Steininger

The Hallimond tube flotation of sphalerite and pyrite with sulfhydryl collectors has been found to be inhibited near neutral pH in the presence of copper salts. Alkalimetric titration studies of the reactions between collector and activator indicate that this effect is apparently related to the formation of basic copper collector complexes. The conditions of formation of these compounds and their stability are in good agreement with the depression observed in flotation experiments. The general procedure employed in the flotation of zinc sulfide minerals requires activation of the mineral surface by heavy metal ions, usually copper, which react more easily than zinc with the common short-chain ionic sulfhydryl collectors.' Commercially, zinc flotation is carried out under alkaline conditions (pH 7 to 10.5), but small-scale experiments indicate that zinc sulfide minerals can also be activated and collected under acid conditions. Selectivity, however, becomes poor at low pH and undesirable materials such as pyrite, silicates and carbonates tend to report in the float. Several years ago, Wark and Sutherland~, measured the contact angles of air bubbles on copper-activated sphalerite immersed in various sulfhydryl collector solutions. When represented, as in Fig. 1, on pH-sodium cyanide diagrams, the results are characterized by 'islands' of non-contact near neutral pH and

Jan 1, 1969

By Carle Hayward

THIS work was first undertaken in the metallurgical laboratory of the Massachusetts Institute of Technology in 1907 by L. A. Dickinson, E. Phelps, and V. S. Rood, under the author's direction. They attempted to determine the diagram for the system Cu2S-NiS, but several inexplicable results were obtained. The following year, P. H. Mayer with Mr. Dickinson carried, on some experiments with nickel sulphide and found that the molten material slowly lost sulphur until it reached a composition corresponding to the compound Ni3S2, established by Bornemann.1 At this point the composition remained stable. The freezing points of the mixtures gradually fell off with the loss of sulphur. Since the above facts seemed to explain the erratic results obtained in the first experiments, Mr. Mayer with F. Jaeger attempted in 1910 to establish a correct equilibrium diagram for the Cu2S-Ni3S2 series. They prepared pure Cu2S and Ni3S2 and determined the cooling curves for various mixtures. The fusions were made in a platinum resistance furnace and the temperatures were measured with a platinum-iridium thermocouple connected with a Sullivan galvanometer. The curve was established for mixtures containing more than 40 per cent. Cu2S, but they were unable to determine certainly the direction of the curve beyond that point. Nothing further was attempted with this series until the present year, when the work was carried to a successful conclusion with the assistance of A. Butts, Jr., and E. H. Weil. The results of this work are given in the following pages.

Jan 1, 1914