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By U. N. Bhrany, N. Arbiter

Over the last one hundred years the problem of assessing the efficiency of energy consumption in producing rock breakage has been studied by many investigators from a variety of viewpoints. Their contributions fall into three main categories: (1) those characterized by a priori assumptions of a relation between the energy required for fracture and the degree of fragmentation produced (e.g. Rittinged(l), Kick(2) Bond(3)); (2) those studying simple systems with controlled energy applications (Gross(4)?(5) ); (3) those treating operating data to develop practical relative measures of efficiency (Coghill(6), Taggart(7)). Closely involved in the efficiency problem is the characterization of size distributions produced by comminution. Unless an experimental size distribution can be approximated by a distribution function and its constants, it becomes difficult if not impossible to develop quantitative energy-particle size relationships. While many such functions have been proposed, none are both completely adequate and convenient. The simpler fonns usually describe only a part of the sizing data, while those which apply to a greater extent are cumbersome(8). The thesis underlying the study here reported can be stated as follows: Size reduction in a tumbling mill subjects ore particles to a relatively constant fracture-producing environment. The intensity of the forces is determined by such factors as the mass of the breaking bodies (rods, balls, rock), and the speed and dimensions of the shell. For a particular ore the extent of size reduction will depend both on the intensity and on the duration of exposure. The latter is the residence time in a batch mill, or is determined by the effective volume and the flow rate in a continuous mill. Size reduction can thus be regarded as a rate process in which the weight of material in size intervals varies as a function of grinding time. Although both the rates of disappearance of coarser sizes and

Jan 1, 1961

By F. C. Canney

Geochemical prospecting seeks hidden mineral deposits by sampling for variations in the chemical composition of naturally occurring materials. Usually the samples are of soils and other products of weathering and erosion—surface materials extremely susceptible to contamination by human activities. Except when a survey is conducted well away from populated areas, contamination is an ever-present hazard. The program's success is particularly endangered when the contaminants are the elements sought; if these occur erratically throughout an area, spurious anomalies completely unrelated to mineralized areas can be formed. Evenly distributed contamination can be dangerous too, if it raises the background to such a level that true anomalies can no longer be easily detected. Suppose, for example, that in an area where the lead background is 20 parts per million the soil over a lead vein contains 1000 ppm of lead. Here the contrast would be 50 to 1, which is very satisfactory for geochemical surveying. Now if 1000 ppm of lead from some source were added evenly to the soil in this area, the contrast would be reduced to about 2 to 1, and the anomaly would no longer be readily detectable because a threshold of significance twice the value of the background is the minimum generally used for interpreting geochemical data. Of the many possible sources of contamination, probably most important are smelter fumes, which may distribute large quantities of metal contaminants over many square miles of ground. For several reasons, the investigation reported here was begun in the Coeur d'Alene district in northern Idaho: 1) a lead smelter has been operated in this district since 1917 and an electrolytic zinc plant since 1928, and presumably the contamination patterns are strongly developed; 2) to evaluate the usefulness of certain geochemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and other veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; 3) one of the economically important parts of the district lies south of the South Fork of Coeur d'Alene River and within a radius of five miles of the reduction plants near Smelterville (Fig. 1). In this area, and in the entire district, conventional methods of prospecting are hindered by heavy vegetation and thick soil cover, and the possibility of contamination by smelter fumes has discouraged geochemical prospecting. Should data reveal that geochemical prospecting could be done successfully in such an area, a particularly useful tool would be available to mining companies and prospectors searching for concealed orebodies in this economically important part of the district. The field work on which this report is based was done from July 28 to 31, 1955. It should be emphasized that this was reconnaissance study only, and therefore far from exhaustive. Previous Investigations in U. S. : The first geochemical survey known to have been affected by contamination was conducted in 1940—a geobotan-ical reconnaissance made in the Michigan copper district by a private company. Geologists found striking variations in the copper content of oak and maple leaves, but unfortunately the high copper isograds of the study seemed to be related more to the Calumet and Hecla copper smelter fall-out than to mineralized ground.' The leaves of one oak tree near the smelter contained 0.4 pct Cu. Similar contamination was reported by Clarke (Ref. 2, p. 41), who conducted experimental geochemical soil and botanical surveys at Ray, Ariz. He found that the leaves of oak trees growing in unmineralized ground near Superior, Ariz., contained more copper than the leaves of oak trees growing on the capping of the Ray orebody and attributed this fact to contamination from the fumes of the Magma smelter at Superior. According to H. E. Hawkes,3 soils and stream sediments in the Superior area are also severely contaminated. Hawkes' work there has shown a copper content averaging 0.5 pct in the surface horizons of soils within one mile of the smelter stack. Samples taken only a few inches below the anomalous surface samples showed only background copper values. In 1950 L. C. Huff' of the USGS made a geochemical survey in an area near Jerome, Ariz., and found considerable zinc and copper in the soils over unmineralized basalt close to Clarkedale, Ariz., and over limestone close to Jerome. As the amounts were notably greater than could reasonably be expected to be derived from the underlying rocks, Huff suspected airborne contamination from the smelter at Clarkedale. Description of Area: The area sampled in detail (Fig. 1) for the study presented here is one of strong relief. The dominant watercourse is the westward-flowing South Fork of the Coeur d'Alene River. East of Kellogg the South Fork flows in a rather narrow canyon, but its valley floor widens considerably to the west where much of the flood plain is covered by an extensive veneer of mining, milling, and smelting debris. South of the South Fork and between Big Creek and Pine Creek is a mountainous area where

Jan 1, 1960

By Charles Will Wright

The present struggle for economic and industrial supremacy by the Communist world is against the United States, its main target, and the other Free World nations. The basis of industrial power is minerals, so the Communist nations are building up mineral production within their borders, often regardless of costs, and are acquiring quantities of mineral products from Free World countries for future use. They are contracting for additional supplies and advancing funds for the development of these quantities. A number of the less developed mineral producing countries of the Free World are being infiltrated by Communists and Communistic influence. This situation is well known, but as yet little has been done to oppose these activities or to awaken the public to their seriousness. The Communist countries are still far behind the Free World Nations in production of many essential minerals. But, shortages are being made up from Free World nations in exchange for petroleum, manganese ore, chromite and other products. Restrictions on shipments of strategic materials to Communist countries have not been maintained.

Jan 1, 1964

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959

By C. M. Smith

DELEGATES from 26 Local Sections and- Divisions of the Institute had three stimulating sessions during the Annual Meeting, a few topics still remaining to be discussed after the two Monday sessions.. The final session was held on Thursday morning. An abstract of the discussion will be transmitted to each delegate present. The topics included: Student relations. Section operation, membership, employment, MINING AND METALLURGY, a new nonmetallic minerals Division. licensing of engineers, and increased allotments of money to Local Sections. Some of the Sections felt that the present limit of $250 allotted to them - from the national treasury was insufficient to carry on their activities, and that this maximum should he increased. A resolution to this effect was passed for transmission to the Board of Directors.

Jan 1, 1935

By J. W. Mills

In 1956 the discovery of nickel on Jumbo Mountain, Snohomish County, Washington, focused attention on this part of the Cascade Range, far more renowned for its timber than for its mineral resources. Hand specimens assaying as high as 13 pct Ni encouraged Discovery Mines Inc. of Mount Vernon, Wash., to stake 12 claims in Township 31 North, Range 9 East of the Willamette Meridian. The property was leased to Climax Molybdenum Co. in January 1957. Trenching, sampling, and geologic studies were carried out during the late summer of 1957 when most of the snow had disappeared. Although the deposits are only about four miles south of the logging town of Darrington and about two miles. as the crow flies, southeast of the end of a good gravel road from that town, all camp supplies and equipment were air-dropped, owing to the extremely rugged nature of the terrain. GEOLOGY The rocks of Jumbo Mountain comprise a series of folded Tertiary sediments forming a belt one half to three quarters of a mile wide, trending northwest about parallel to the strike of the beds. This belt is sandwiched between two extensive in-trusives—gabbro on the northeast and quartz dio-rite on the southwest—and has been intruded by dikes of fresh and serpentinized dunite. Shear zones follow many of the dunite-sedimentary rock contacts, and in these the nickel mineralization is concentrated. A few transverse faults offset the sediments and ultrabasics. Sedimentary Rocks: Two kinds of quartzite make up the greater part of the sedimentary section. One is dark purplish gray, very fine-grained, and thin-bedded; the other is light gray to white, medium-grained, and well-bedded. Locally the light-colored quart lites contain grit and conglomerate horizons, rich in pebbles of white chert and very fine-grained quartzite. Intercalations of dark argillites near the summit of the mountain give many of the cliffs a striking banded appearance. Dark gray to black, aphanitic, thin-bedded argillites occur throughout the entire sedimentary belt. Beds vary from a few inches to a few tens of feet thick and some, near the summit, contain numerous fossile (willow?) leaves. Only the thicker beds were mapped. The sediments are quite fresh on the northeastern side of the belt and become more metamorphosed (hornfelsed) toward the southwestern side. Brown biotite is present in the metasediments in increasing amounts as the quartz diorite is approached. Near the intrusion, porphyroblasts of plagioclase, up to 1 in. across, testify to the soaking of sedimentary rocks by solutions emanating from the quartz diorite. Most of the sediments mapped lie along the southwestern limb of an anticline, the axis of which follows the crest of the mountain and plunges at a low angle to the northwest.

Jan 1, 1961

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By Jay A. Carpenter

THIS preliminary report from the Committee to Study Relations Between Students and the Institute is submitted to our member- ship for consideration and discussion before the general subject comes up for action at the Annual Meeting in February. At present, the A. I. M. E. has a dual relationship with mining students, each relationship in no may connected with the other. To the individual student the Institute offers for $2 a year a Student Associateship in the Institute which carries with it a subscription to MINING AND METAL- 'LURGY, a watch fob, and the privilege of becoming a Junior Member after graduation without payment of the -first year's dues, if one's application is accepted. To the student's college society it offers the privilege, upon application, of becoming 'an Affiliated 'Society, which brings with it no specific supervision or aid, and in turn requires no specific conditions as to membership, fees, or rules. This Affiliated Society is distinctly a school organization which Student Associateship in the Institute can he given special status or ignored, is the local .society sees fit.

Jan 1, 1934

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

Jan 1, 1965

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By AIME AIME

THE week, of April 5 will long be remembered by those that attended the Birmingham meetings of the Open-Hearth and Blast Furnace committees of the A.I.M.E. Iron and Steel Division. Birmingham iron and steel own received the 450 delegates with open arms; described and discussed their southern metallurgical practices and problems and compared experiences with their northern brother metallurgists in two days of technical sessions on Wednes-

Jan 1, 1937

By J. E. House, C. J. Lewis

In the solvent extraction process, also referred to as liquid-liquid extraction, the clarified uranium-pregnant sulfuric acid leach solution is contacted with an organic extractant dispersed in kerosene; the uranium enters the organic phase and associates itself with the organic extractants. Simultaneously an-ions or cations, as the case may be, leave the organic extractant phase and enter the aqueous phase. The two phases are then allowed to separate by virtue of their immiscibility. Based on the data available, a generalized procedure for the recovery of molybdenum from the sodium carbonate scrub liquor of acid leach uranium mills using secondary and tertiary amine extractants is presented, as is another generalized procedure for the recovery of molybdenum from the bleed stream of alkaline leach uranium mill circuits. Such economic appraisal as can be made at this stage of the development is also indicated. Molybdenum occurs in most uranium ores. Whether the uranium is solubilized by the acid leach route or by the alkaline leach process, some of the molybdenum present in the ore is solubilized along with the uranium. Molybdenum in uranium mill pregant solutions may cause processing difficulties, among which may be mentioned the poisoning of resins, the precipitation of organo-molybdenum complexes, or the build-up of molybdenum in recycle streams. While the uranium milling industry has been successful in applying measures to overcome the problems arising from the presence of molybdenum in the circuits, such measures nevertheless add to the cost of producing uranium yellow cake concentrate. Table I shows the analysis of typical uranium pregnant leach solutions. Uranium recovery by solvent extraction is presently practiced only in conjunction with acid leach circuits, and it may be noted that of about 16,000 tons of uranium ore daily processed by sulfuric acid leach, more than half of this tonnage follows the solvent extraction route. Uranium mills leaching ore with sodium carbonate-sodium bicarbonate solution (the so-called alkaline leach circuit) do not use solvent extraction. In this case the uranium pregnant solution is sufficiently pure to permit the direct precipitation of uranium concentrate with subsequent recycle of the alkaline leach solution. While solvent extraction procedures may be developed which are economically attractive for the alkaline leach uranium process, this has so far not been the case. The earlier uranium mill solvent extraction circuits used organo-phosphate extraction reagents, among which di-2-ethylhexyl phosphoric acid was popular. It should be borne in mind that uranium in its sulfuric acid leach solution exists in an equilibrium involving uranium in both anion and cation forms: uo + 2S0 = [uo2(so4)2] For this reason uranium may be extracted by either cation extractors or anion extractors and this is likewise true of molybdenum. However, the organo-phosphate extractants also load ferric iron which is usually present in the uranium acid leach solution. For this reason, it is necessary to reduce this solution substantially to the ferrous state ahead of solvent extraction using organo-phosphate reagents. The amines, being anion extractors, selectively reject iron and thus render the iron reduction step unnecessary. In the solvent extraction process, also referred to as liquid-liquid extraction, the clarified uranium-

Jan 1, 1961

By L. B. Davidson

The petroleum literature contains many reports on the relative permeability properties of porous media. However, only recently have studies of relative permeability at elevated temperatures been made.1 -5 Each of these studies presents relative permeability data on water-oil systems in linear sandpacks or sandstone cores under isothermal conditions. The results of these investigations are dissimilar. Edmondsonl found that in Berea sandstone a temperature-dependent effect was present, while Shilobod,2 using the same material, found no temperature dependence after normalizing for initial water saturation. Workers at Texas A&M U.3-5 found that the ratio kw/ko was temperature dependent in an unconsolidated system. The differences in results of these studies are probably a consequence of differences in the material employed, in the experimental procedures followed, and in the properties of the porous systems used. This paper describes an experimental investigation of permeability ratio temperature dependence, conducted to clarify some of the results obtained by previous workers. Each experiment described in this paper involved the isothermal displacement of Chevron No. 15 white oil by either nitrogen, steam, or distilled water and displacement of water by nitrogen. All permeability ratios were calculated using the Welge procedure. Values of the water-oil permeability ratio were obtained over the temperature range 75OF to 540°F. Results indicate the ratio is temperature dependent at low water saturations, probably due to interfacial effects. However, as the saturation is increased, temperature dependence decreases until, above some minimum saturation, the ratio becomes insensitive to temperature. Previously published work indicates that the dependence reappears at very high water saturations, a region of the ratio curve not completely examined in the present study. It appears that water-oil permeability ratios are temperature dependent at the extremes of the ratio curve where changes in interfacial tension with temperature induce variations in residual saturations. Between the extremes, there is a region in which the permeability ratio is insensitive to temperature. The size and location of this region is probably a function of the characteristics of the porous system. Gas-oil permeability ratios calculated from nitrogen-white oil displacement experiments indicate a definite temperature dependence over the range 75OF to 500°F and over the entire gas saturation range studied. Evidence discussed in this report indicates that this dependence is a consequence of molecular slippage in the gas phase. This is an extension of the Klinkenberg effect6 to two-phase systems at high temperatures (the existence of slippage in two-phase systems at room temperature has been demonstrated7). Evidence for a similar source of temperature dependence in superheated steam-white oil experiments

Jan 1, 1970

By David White

Jan 1, 1925

By AIME

SUPPLEMENTING surveys of the engineering profession regarding salaries and advancement, based upon data from individual engineers, a survey through a questionnaire to employers of engineers has recently been made by a subcommittee of the Engineers Joint Council's Committee on the Economic Status of the Engineer. Its object was to learn directly from employers their attitudes and policies pertaining to the selection, training, placement, advancement, guidance, and professional activities of engineering graduate employes. The questionnaire was sent in May 1946 to 174 employers of engineers, including colleges. Replies were received from 104 employers in nineteen fields of industry, who employ about 2,000,000 persons, about 40,000 of whom are engineers. The following general observations are based on the questionnaires returned. Who Are Hired? Of the co-operators 96 per cent employ cadet engineers directly upon graduation from engineering schools, but only 4 per cent recruit their engineering staffs exclusively from the new graduates. About 43 per cent hire more than half of their new engineer employes after one or more years' experience with other employers. This is evidently a matter of necessity or expediency rather than preference, because more than sixty per cent of those reporting indicate that they prefer to hire the new graduate.

Jan 1, 1947

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By Arnulf Muan, Egil Aukrust

Activities of COO in the three solid solution series COO-MgO, COO-MnO, and COO-"FeO" have been determined at 1200°C by equilibrating oxide samples with a metal phase (cobalt or a Co-Fe alloy) in atmospheres of known oxygen activities. The systems COO-MgO and COO-MnO are ideal, within limits of experimental error, whereas the system COO-"FeO" shows a slight positive deviation from ideality at the temperature of this investigation. KNOWLEDGE of activities of oxide components in solid solutions is necessary for the calculation of the cation distribution among coexisting oxide phases in many important metallurgical, ceramic, and geochemical systems. Very few activity-composition curves are available for such systems at the present time. A start on the prodigious job of obtaining such data has been made by studies of solid solutions with simple sodium chloride type structure containing NiO or "FeO" as a component.1-3 The present paper describes similar studies for solid solutions with sodium chloride type structure containing COO as a component. For the systems COO-MgO and COO-MnO, the activity solid solution is determined by the equation Here po and are the oxygen activities of the gas phase in equilibrium with the phase assemblages metallic cobalt plus oxide solid solution, and metallic cobalt plus pure COO, respectively. In the system CoO-"Fe07', the metal phase is a Co-Fe alloy rather than pure cobalt. In this case the activity of COO in the oxide solid solution is calculated from the equation where a& is the activity of cobalt in the metal phase. Because the system Co-Fe is close to ideal4 and the metal phase appearing in the present work contains less iron than cobalt even at the lowest COO concentrations of the oxide phases used may be set equal to N . Hence, Eq. [2] becomes The value of Nc, can be estimated from the relative stabilities of the oxides COO (see below) and I) EXPERIMENTAL METHOD Two different but closely related procedures were used in the present investigation to determine the activity-composition curves. In one method, the oxide solid solutions were equilibrated against

Jan 1, 1963

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By J. W. MacDonald

Review of equipment, performance, and shaft design plans including head-frames for sinking and forms for lining are given. Also included are comparative data for shafts of 11 x20 ft and 193/4 x 30 ft with 756 and 666-ft depths, respectively. Advantage from curtain wall installation with "slip forms" which warrant consideration for normal lining are outlined. A preliminary review is also made of "chemical grouting" to stop water inflow leakage with Halliburton equipment and service. Two coal mine shafts recently completed in Franklin County, Ill., afford experience and accomplishment to warrant review. These shafts provide access to a tract with a potential recovery of one hundred million tons. This work provided the initial sinking by other than a contractor's organization since 1918. Four additional shafts required during the interim were sunk under contract arrangement with others. Supervisory contact and inspection afforded experience to govern planning and conduct of the recent work. TEST DRILLING Core test holes were drilled within each of the two shaft locations. Four additional cable tool holes were drilled on a radius of 700 ft from the shaft bottom to determine the coal seam elevations and govern the underground layout plans for each shaft. A graphic log of the hoist shaft test drillhole is shown by Fig. 1. A very soft sandstone was found at a depth of 16 ft. Cored recovery of the sandstone proved much weaker than the overlying compacted sand secured with coring facilities for soil recovery. Gradation from the very soft sandstone to fairly hard material occurred with the next 14 ft, extending to a depth of 30 ft. The weak character within the upper portion entailed need of adequate protection when sinking as described later. A part of the sandstone provided sufficient porosity and permeability to warrant further investigation. Adjacent cable tool drilling for temporary water supply disclosed inflow was limited to 2 gpm with a depth of 40 ft. It was increased to 12 gpm during the next 50 ft of drilling and occasioned subsequent precaution when sinking. General arrangement of facilities for sinking the hoist shaft is shown by Fig. 2. An available steel frame building was used to accommodate the hoist, compressor, shop, and shower or change room. The stiff leg derrick with 90-ft length of boom permitted removal of forms from the wood shop to the storage area or delivery within the shaft. Reinforcing steel and other needs were similarly handled, in addition to headframe erection. The headframe was placed over one end of the shaft to enable passage of forms for lining through the adjacent half next to the stiff leg derrick. The steel headframe as shown by Fig. 3 was fabricated locally. Side anchored cables from the

Jan 1, 1961