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By Franz R. Dykstra, R. F. Tatnall

A ferroalloy is defined as: "An alloy of iron with some element other than carbon used as a vehicle for introducing such an element into the manufacture of steel. The element may alloy with the steel by solution or, as the carbide, -neutralize the harmful impurities, by combining with them and separating from the steel as flux or slag before solidification."a The most commonly used ferroalloys are: ferromanganese, ferrochrome, ferrosilicon, ferrovanadium, ferromolybdenum, ferronickel, ferrotungsten, ferrocolumbium, and ferrophosphorus. Concern here is with the sources and markets of the major metallic alloying elements. The discussion is further restricted to those - ferroalloy ores, the principal use of which is in the production of steel. Phosphorus, silicon, and tungsten, for example, are ferroalloys of some economic significance, but other uses dwarf their alloying applications. Thus, this discussion will deal with the ores of managanese, chromium, nickel, molybdenum, vanadium, and columbium. As shown in Table 14.1B.1 ferroalloys serve to- facilitate processing and impart to the finished steel such characteristics as tensile strength, ductility, low-temperature impact, hardenability, high-temperature strength, corrosion resistance, toughness, and abrasion resistance. In the steel-making process, ferroalloys may be added in the charge, in the molten bath near the end of the finishing period, in the ladle, or in the molds. Timing of the addition depends on the effect of the addition on the temperature of the molten metal, the formation and elimination of reaction products, and the protection of subsequent additions from oxidation. MANGANESE General Approximately 95% of the manganese ore sold is consumed by the steel industry, either as ferromanganese or as manganese metal. Manganese is the universal alloy, without which good steel cannot be made. It serves as a scavenger, removing phosphorus, sulfur and, to a degree, oxygen from the melt. As an alloying material it makes steel hard, tough, and resistant to wear. Approximately 6 kg of manganese is required for every ton of common steel produced by United States steelmaking practice. The remaining 5 % of the manganese ore consumed consists of special or so-called "chemical" ores, including high-grade pyrolusite ores, electrochemically reactive "battery ores," and a number of special varieties, as well as those otherwise regarded as "metallurgical ores."

Jan 1, 1976

By A. G. McGregor

DURING the past 5 years, five new copper-smelting plants have been built and put into operation in the State of Arizona. The monthly copper output from these plants averages from 5,000,000 to 18,000,000 lb. Previously, there never was as much activity in copper-smelting plant construction in the same length of time in all the rest of the world. Naturally, in this amount of work, some new problems were met and new features in plant design and. equipment developed. Some of these features are described in this paper. CONCENTRATE HAULING, UNLOADING AND SAMPLING SYSTEM (a) Concentrate Car The International Smelting Co. has provided at its plant at Miami specially designed cars for hauling the concentrates from the mills of the Inspiration Copper Co. and the Miami Copper Co.. The car has a bottom that is readily made tight to hold flotation concentrates and is quickly and cheaply unloaded. Figs. 1, 2 and 3 show views and details of the car. The main feature of this car is the slot in the bottom throughout its length, which is closed by means of short planks that overlap like ship-lap as shown by Fig. 1. At one end of the car an iron gate operated by a screw and hand wheel is provided, which clamps or presses the planks together, making the bottom tight. A removable tapered plug rests vertically over this gate when the loading of the concentrates at the mill commences.

Jan 8, 1916

By W. Edeburn, H. R. Fife

An extended study of dustproofing Freeport-seam coal has emphasized several fundamental features in the successful treating of bituminous coals. The extent of the exposed surface area and its absorption propcrties for the dust-retaining film were found to be the most critical factors affecting the efficiency of fly-dust prevention. From recently published screen data and specific surface-area measurements on United Kingdom coals, an approximation of the surface exposed by mine-run coal and by 1-in. slack was made. The total surface area exposed by an average tori of this mine-run coal was estimated at 3768 sq. yd., while a ton of 1-in. slack represents a total surface area of 8779 sq. yd. with no additions for porosity. It is important in coal treating to consider that in mine-run coal the fraction above 1/4 in. in size represents 79.5 per cent of the total weight, but only 4 per cent of the total surface, while the fraction below 150 mesh contains 47 per cent of the total surface and only 1.2 per cent of the total weight. Also, one should appreciate that, in a 1-in. slack, the domestic stoker fraction (1 in. to 8 mesh) contains 76.3 per cent of the weight and 8.2 per cent of the surface, while the fraction below 150 mesh represents 3.3 per cent by weight and 54.8 per cent by surface area. Wax extraction data on 1-in. to 0 slack from mine-run treated Freeport-searn coal showed that the coating was distributed uniformly as a function of exposed surface; hence, nonuniformly on a weight basis. This distribution of the coating on mine-run coal therefore limits the extent of treating that is desirable on bituminous coal at this point in the preparation. The treatment of Freeport mine-run coal before it reached the tipple gave a 70 to 80 per cent reduction of fly-dust in the tipple, a satisfactory treated commercial slack coal, and an indicated change in the trend of tipple degradation. The premium-treated domestic sizes required a supplemental treatment for complete dustproofness. The actual cost of the pretipple and supplemental treatments was very low per ton of coal treated, while the net or true cost was sufficiently

Jan 1, 1938

By A. W. Allen

The technological study of the treatment of gold and silver ores has been largely responsible for the phenomenal strides which have marked the progress in this branch of metallurgy during recent years. In no other application of science to industry is system more imperative at every stage; correct formulation of result is only second in importance to efficiency of operation. Progress in method, on the other hand, is mainly due to individua1 initiative aided by the work of technical journals and metallurgical societies. There still remains a field for profitable discussion, and it is my intention to deal with some inconsistencies of expression common to a number of writers on the subject; and also to draw attention to the false impressions created by a statement which may, possibly, be only unintentionally misleading. I also take the opportunity of tracing the source of both metallurgical and economic result; and would question the desirability of the methods usually employed in arriving at a final statement. In the first place, I wish to deal with the question of extraction. This term may mean anything or nothing, and it is often used to mislead. In a report of a mining engineer as to the result of operations subsequent to the remodeling of a treatment plant prominence was given to the statement that the extraction had amounted to 91 per cent. On examination it was found that only a small percentage of the so-called extraction was calculated on actual bullion return, a proportion being figured from the gold left in the zinc boxes, and not recovered. In addition to this, a proportion of the extraction was said to be due to gold in concentrate. As there was no conrcentrating apparatus on the property and as concentration did not form a part of the scheme of treatment the matter was investigated, with the result that the concentrate, of lower gold content that the original ore, was found to be the result of an inegcient pumping system which failed to provide for the whole of the battery product delivered to it. The balance was stacked and, although itself of no marketable value, the gold content was allowed to form a basis of extraction figures. The illustration may be extreme, but it will serve to show to what lengths an engineer may go in the mutilation of the most vital term in metallurgical technology.

Jan 1, 1915

By W. Edeburn, H. R. Fife

An extended study of dustproofing Freeport-seam coal has emphasized several fundamental features in the successful treating of bituminous coals. The extent of the exposed surface area and its absorption propcrties for the dust-retaining film were found to be the most critical factors affecting the efficiency of fly-dust prevention. From recently published screen data and specific surface-area measurements on United Kingdom coals, an approximation of the surface exposed by mine-run coal and by 1-in. slack was made. The total surface area exposed by an average tori of this mine-run coal was estimated at 3768 sq. yd., while a ton of 1-in. slack represents a total surface area of 8779 sq. yd. with no additions for porosity. It is important in coal treating to consider that in mine-run coal the fraction above 1/4 in. in size represents 79.5 per cent of the total weight, but only 4 per cent of the total surface, while the fraction below 150 mesh contains 47 per cent of the total surface and only 1.2 per cent of the total weight. Also, one should appreciate that, in a 1-in. slack, the domestic stoker fraction (1 in. to 8 mesh) contains 76.3 per cent of the weight and 8.2 per cent of the surface, while the fraction below 150 mesh represents 3.3 per cent by weight and 54.8 per cent by surface area. Wax extraction data on 1-in. to 0 slack from mine-run treated Freeport-searn coal showed that the coating was distributed uniformly as a function of exposed surface; hence, nonuniformly on a weight basis. This distribution of the coating on mine-run coal therefore limits the extent of treating that is desirable on bituminous coal at this point in the preparation. The treatment of Freeport mine-run coal before it reached the tipple gave a 70 to 80 per cent reduction of fly-dust in the tipple, a satisfactory treated commercial slack coal, and an indicated change in the trend of tipple degradation. The premium-treated domestic sizes required a supplemental treatment for complete dustproofness. The actual cost of the pretipple and supplemental treatments was very low per ton of coal treated, while the net or true cost was sufficiently

Jan 1, 1938

By W. R. Bull, J. R. Roos

A method is described whereby the true financial value of each constituent of each concentrate can be calculated. Each value is then compared with what this value would be in a perfect separation. The difference in each case represents the loss incurred by each aspect of an inefficient separation. The relative magnitudes of these losses indicate those avenues of plant investigation and research that offer the highest potential reward. The metallurgical efficiency of a concentration operation is difficult to express because there are two criteria of performance, namely, grade and recovery. Neither of these alone gives any indication of the effectiveness of an operation and, if they are combined in some formula, it must be empirical and unreliable because of many external factors. Since milling is an operation performed as one step in the most profitable overall method of producing a metal or other end product, the main objective of mill operation should be to make a maximum contribution to this maximum profit. When concentrates are sold to custom smelters, the income from the operation, and the costs, may be calculated. When concentrates are further processed by another division of the same company, and there is no formal financial relationship between, say, the milling and smelting divisions of the company, the mill superintendent's job is less well defined. But even so, if the mill superintendent works as though he were selling his concentrates, and uses reasonable, if fictitious, conditions of sale, then he can get a good indication of the effectiveness of his operation by calculating his "Economic Recovery". ECONOMIC RECOVERY This is a method used as a basis of operation by several mills and has been described in the literature. Very briefly, the "standard" of operation is taken as that of a mill separating the ore into perfectly pure concentrates with 100% recovery of each mineral in its respective concentrate. For example, a 4%Pb, 4% Zn ore (galena and sphalerite), would provide a lead concentrate weighing 4.62% of the feed and assaying 86.6% Pb and a zinc concentrate weighing 5.97% of the feed and assaying 67.1 % zinc. These perfect concentrates are (hypothetically) shipped to the appropriate smelters, freight and treatment charges and payments calculated, and the net return obtained. This is the optimum financial return for the operation of the mill and is used as the standard. Now the return for the actual, real-life, mill operation is calculated in the same way, and the ratio of the two is termed the Economic Recovery. Many additions and modifications may be made in any particular case. For example, if the zinc mineral is marmatite, the optimum grade of the zinc concentrate may be set lower than 67.1%. If silver is present, it will be recovered 100% in the lead concentrate in the perfect operation. Similarly, cadmium will be recovered 100% with the sphalerite. Mr. Weiss' paper' mentions a case where, because of extremely fine intergrowth between the valuable mineral, chalcocite, and pyrite, the optimum grade of copper concentrate was taken as 45% Cu instead of the theoretical 80%. Each operation will present its own possibilities in this way.

Jan 1, 1970

Jan 1, 1888

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1941 are available at Institute headquarters, unless otherwise noted They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS TECHNICAL PUBLICATIONS in Classes A-Metal Mining, 13-Milling and Concentration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETROLEUM TECHNOLOGY, which is issued every other month TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysics, are issued as separate pamphlets An Institute member is entitled to one copy of any printed TECHNICAL PUBLICATION or CONTRIBUTION Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute according to their registration by classes CONTRIBUTIONS and other TECHNICAL PUBLICATIONS will be sent upon request A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page, minimum charge, 25¢ Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1 25 domestic, $1 35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2 50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7 80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers) MINING TECHNOLOGY, $6 per annum domestic, $6 60 foreign (metal mining, milling and concentration, Industrial Minerals Division, and mining geology papers) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6 60 foreign Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY Is mailed each month A member is entitled to one volume a year on his membership and he may purchase for $2 50 one copy of a volume not already received, additional copies of the same volume, $5 Nonmembers in the United States may purchase the volumes listed at $5 each, outside of the United States and its possessions, $5 6o Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 500 each to members, to nonmembers 50¢ current issue and $1 each, back issues Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4 00 foreign.

Jan 1, 1941

By R. C. Craze

During the past 20 years. research and development in the study of reservoir behavior have dealt principally with flow of oil through sandstones. Many reservoir studies of sand fields have proved valuable in promoting recovery efficiency. This paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone reservoir studies to the study of limestone reservoir performance. The characteristics of limestone porous systems, porosity-permeability relationships, distribution and occurrence of oil, and characteristics of flow through such systems are discussed. Recognition is made of the similarities or differences which these factors exhibit in limestone and sandstone systems. Comparisons between operating data for typical limestone and sand reservoirs are presented. It is indicated that the distribution and movement of fluids in and through porous limestones follow the same fundamental principles underlying such processes in sandstones. This fundamental similarity may readily be discernible in the performance of many limestone reservoirs. The volumetric balance and unsteady state radial flow equation, the fluid displacement equation, use of electrical analogue devices, and other analytical techniques to study the behavior of limestone fields appear fundamentally applicable, but do require thorough understanding of the properties of the formation, of the fluids, their behavior during flow, and adequate production operating data. Need for more complete coring and comprehensive examination of core properties is stressed. The results of "active oil" studies, and of flow and interference tests are presented. Well spacing, well completion, and efficient rates of production in limestone reservoirs are briefly discussed. INTRODUCTION Limestone and dolomite reservoirs constitute the largest source of supply of crude oil in the world. an estimated 60 per cent of present production coming from carbonate reservoirs. In many large geologic provinces such as Mexico. the Middle East, and more recently Canada, almost all the oil is found in this type of rock. In the United States, all of the major oil-producing areas except California and Pennsylvania contain oil-bearing carbonate formations. The discovery in recent years of large oil reserves in the Silurian, Devonian, and Ordo-vician formations in West Texas, in addition to the large reserves in the Permian, has accentuated the interest of operators, geologists, and engineers in limestone formations and in the many problems associated with understanding the performance of these reservoirs. The rapid increase in discovery of oil in limestone formations and the present-day position of prominence held by these fields in the production and reserve picture in all parts of the world emphasize the horizons opened to the reservoir technologist in the field of geological and production research. Pertinent to an interpretation of the behavior of limestone reservoirs are the methods of analysis which may be utilized and a possession of full knowledge of the many factors which influence the analytical procedures. During the past 20 years a well-developed science of reservoir engineering has been built upon the research of many workers who studied the fundamental nature of oil reservoirs, characteristics of the porous media, properties and behavior of the contained fluids, and the mechanics of flow. Application of these studies to production practice has resulted in greater recoveries and more efficient field operation. The major portion of this evolutionary process has been founded upon studies of sand fields. The applicability of these more thoroughly developed techniques for studying sand fields to the study of the behavior of limestone fields becomes a factor of technical and practical significance. In the light of the technological background available to the reservoir analyst, this paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone studies to the study of limestone reservoir performance. LIMESTONE RESERVOIR CHARACTERISTICS The characteristics of limestone and sandstone reservoirs are similar in many respects and they both may occur under similar structural conditions. Fundamentally, the distribution and movement of fluids in and through the porous limestone media follow the same basic principles which dictate such processes in sandstones. Herein lies a fundamental similarity, which may readily be discernible in the performance of many limestone reservoirs. In some limestone fields, as in many sand fields, widely varying formation properties and distribution may reveal themselves in deviations in the performance of the reservoir, in the behavior of wells, and in fluid flow through the rock, and make difficult the delineation of reservoir behavior. Only by reservoir studies, core analyses, and coordinated laboratory and field experimentation can the effects of the many influencing factors upon the nature of limestone production be determined. FORMATION CHARACTERISTICS The chief difference between limestone and sandstone, aside from their chemical compositions, is the difference in the geometry and origin of the porous systems in the two kinds of rock. In sandstone the porous system results entirely from the openings among individual sand grains which occur during deposition. The geometry of the openings between the sand

Jan 1, 1950

By H. W. Hitzrot

SEPARATING a mixture of particle sizes of material suspended in a liquid medium is by no means an exact science. Selecting machines for individual classifying operations is even more difficult. The plant operator's own background is of course invaluable, and considerable help may be obtained from technical articles, talks with sales engineers, and handbooks on ore dressing. These several sources of information, however, are difficult to marshal in proper perspective for the major decision on classification units that an operator may be called upon to make. To the present writer's knowledge this assembly of facts is not available in handbooks, and technical papers are scarce on classification equipment developed in the past five or six years. It is believed that this paper will be helpful to users of classification equipment at this particular period in the development of hydro-classification. For easy reference the following classification units now available and in use in metallurgical and industrial operations are listed below, with a brief description of each. Unit-type classifiers, bowl classifiers, and bowl desiltors are all rectangular tanks, slightly tilted, with reciprocating rakes or screws to remove settled sands. The unit-type classifier, Figs. 1 and 2, is available in widths from 14 in. to 20 ft and lengths up to 40 ft. The shallow bowl of the bowl classifier, Fig. 3, equipped with rotating rakes, is superimposed on the lower end of the tank. Reciprocating rake compartments for this design range from 18 in. to 20 ft wide. Bowl diameters vary from 4 to 28 ft. The flat-bottomed bowl of the desiltor, Fig. 4, of relatively large diameter, is equipped with rakes rotating outward and partly over a pit, which is created by extension of the rectangular tank into and under the bowl section. Bowl desiltors are available with reciprocating rake sections 4 to 20 ft wide and bowls from 20 to 50 ft in diam. The bowl desiltor is used for applications beyond the range of the bowl classifier. The hydroseparator, Figs. 5 and 6, is a circular tank equipped with slowly rotating rake arms, set on a slope, with interrupted rake or spiral blades to move the settled solids to a central discharge cone. Tank diameters vary from 4 to 250 ft. Tank depths at center are 2 to 3 ft for small units and up to 25 ft for larger units. Hydraulic classifiers of the sizer and super-sorter types, Figs. 7 and 8, are narrow, deep, rectangular tanks divided by vertical baffles into a series of pockets. Hydraulic water is added near the bottom of each pocket. Perforated constriction plates, spiral flow arrangements, or jets are used to disseminate the water under pressure (hydraulic water) throughout the bed of material in the pocket. Discharge valves on each pocket are operated automatically by a pneumatic mechanism, a pincer-type mechanism, or a pressure control and motor combination actuated by a hydrostatic tube within the pocket. Hydraulic classifiers are available in 4, 5, 6, and 8-pocket units of varying constriction plate areas to suit conditions. There is now a jet sizer of unit pocket design that can be made up in 1 to 25 sections or more to accommodate sizing requirements. The hydroscillator, Fig. 9, is a rectangular tank set on a slope of 3 to 4 in. per ft. A bowl is superimposed on the lower end. The bowl bottom is an oscillating rubber-covered disk, perforated to allow hydraulic water introduced beneath the disk to set up a teeter bed and thus produce an oversize or rake product exceptionally free of slimes, and material minus the mesh of separation. A shallow dam at the periphery of the bowl allows the coarse or oversize fraction to spill over and drop down into the tank compartment, where it is moved up the deck by reciprocating rakes. The material, minus the mesh of separation, overflows a circular and stationary weir which is several inches higher than the dam on the oscillating disk. It is carried off in a circular launder in the usual manner. These units are available in bowl diameters from 4 to 14 ft and with reciprocating rake compartment widths to suit the tons per hour to be handled. Centrifugal classifiers include the solid bowl centrifuge and the cyclone classifier. The solid bowl centrifuge, Fig. 10, consists of a truncated cone fixed to a horizontal shaft and rotating at high speed. An internal spiral rotating at slightly less speed continuously removes solids deposited on the inner surface of the cone, or bowl. Feed enters the cone by means of the hollow center shaft. Overflow leaves through ports at the large end of the cone, and oversize solids, moved by the spiral, exit through ports at the small end. Centrifugal classifiers of this type are available in cone diameters from 18 to 54 in. The cyclone classifier, Fig. 11, is a stationary cone having a cylindrical upper section and a lower cone section. Feed is introduced tangentially into the upper cylindrical section under pressure from a hydrostatic head or by means of a pump. Centrifugal force thus induced effects a classification within the cone, the fine sizes being carried off in the overflow through an opening at the top of the cylindrical section. Coarse solids at relatively high pulp density exit through a control valve at the apex of the lower cone section. Cyclone classifiers are available in 3, 6, 12, 14, 24, and 30-in. diam. The cone classifier, Fig. 12, is a steel-plate cone with sides usually about 60" from horizontal. It contains no rotating mechanism. Feed enters a feed-well at center and classification is effected by gravity and pulp density. Fines are carried off in the flow over a peripheral weir at the top of the cone. Settled solids exit through an opening at the apex. An apex valve actuated through levers and rods by the pulp density in the lower cone section is usually supplied. Diameters are usually maximum at 8 ft.

Jan 1, 1955

October 16th, 1872. THE Institute assembled on Wednesday evening at the Western University, and was called to order by President Raymond. Mr. James Park, Jr., of Pittsburgh, made the address of welcome, which was responded to by President Raymond. The Council reported the following names, with approval, for election Ashburner, William, - San Francisco, Cal. Asmus, George, - New York. Baillie, Nathaniel, - Uniontown, Pa. Bowie, A. J., Jr. - San Francisco, Cal. Brown, A. J., - Treasure City, Nev. Butler, J. G., Jr., - Youngstown, Ohio. Chamberlin, J. G., - Leetonia, Ohio. Clark, R. Neilson, - Canyon City, Colorado. Cornell, A. B., - Youngstown, Ohio. De Crano, E. G., - San Francisco, Cal. Engelmann, H., - Salt Lake City, Utah. Faber du Faur, A., - New York. Janin, Louis, Jr., - San Francisco, Cal. Johnson, George J., - Salt Lake City, Utah.. Kent, Joseph C., - Phillipsburgh, N. J. Kent, William St. G., - Phillipsburgh, N. J. Liebenau, Charles von, - Silver City, Idaho. McClintock, A. H., - Wilkes-Barre, Pa. Miller, Thomas N., - Pittsburgh, Pa. Millholland, James A., - Mount Savage, Md. Peters, Ed. D., Jr., - Dudley, Colorado. Reese, Jacob, - Pittsburgh; Pa. Schirmer, J. F. L., - Denver, Colorado. Smith, W. S., - Fairplay, Colorado. Stoelting, Hermann, - Georgetown, Colorado. Sweet, W. A., - Syracuse, N. Y. Tripple, Alexander, - New York. Van Arsdale, W. H., - Swansea, Cal. Willard, Dwight D., - Bordentown, N. J. The following resolution was then offered and passed Resolved, That gentlemen present, not members, be invited to take part in the discussions of the Institute at the various sessions of the present meeting.

Jan 1, 1873

TEE Institute assembled on Wednesday evening at the Western University, and was called to order by President Raymond. Mr. James Park, Jr., of Pittsburgh, made the address of welcome, which was responded to by President Raymond. The Council reported the following names, with approval, for election : Ashburner, William, . . . . . San Francisco, Cal. Asmus, George, . . . . . . New York. Baillie, Nathaniel, . . . . . Uniontown, Pa. Bowie, A. J., Jr., . . . . . San Francisco, Gal. Brown, A. J., . . . . . . Treasure City, Nev. Butler, J. G., Jr., . . . . . Youngstown, Ohio. Chamberlin, J. G., . . . . . Leetonia, Ohio. Clark, R. Neileon, . . . . . Canyon City, Colorado. Cornell, A. B., . , . . . . Youngstown, Ohio. De Crano, E. C., . . . . . San Francisco, Cal. Engelmann, H., . . . . . . Salt Lake City, Utah. Faber du Faur, A., . , . . . New York. Janin, Louie, Jr., . . . . . San Francisco, Cal. Johnson, George J., . . . . . Salt Lake City, Utah., Kent, Joseph C., . . . . . Phillipsburgh, N. J. Kent, William St. G., . . . . Phillipsburgh, N. J. Liebenau, Charles von, . . . . Silver City, Idaho. McClintock, A. H., . . . . . Wilkes-Barre, Pa. Miller, Thomas N., . . . . . Pittsburgh, Pa. Millholland, James A., , . . . Mount Savage, Md. Peters, Ed. D., Jr., . . . . . Dudley, Colorado. Reese, Jacob, . . . . . . Pittsburgh, Pa. Schirmer, J. F. L., . . . . . Denver, Colorado. Smith, W. S., . . . . . . Fairplay, Colorado. Stoelting, Hermann, . . . . . Georgetown, Colorado. Sweet, W. A., . . . . . . Syracuse, N. Y. Tripple, Alexander, . . . . . New York. Van Arsdale, W. H., . . . . . Swansea, Cal. Willard, Dwight D., . . . . . Bordentown, N. J. The following resolution was then offered and passed : Resolved, That gentlemen present, not members, be invited to take part in the discussions of the Institute at the various sessions of the present meeting.

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By S. C. Sun, John A. L. Campbell

Objective of the ittvestigation was to determine the electrokinetic differences, if ally, of anthracite lithotypes and thus establish the feasibility of making a coqlstituent separation by froth flotation or other surface-dependent processes. The elec-trokinetic properties were determined by streaming potential methods. In addition, chemical and physical analyses of the lithotypes were made to establish nonsubjec-tive parameters for their diflerentiation. Electrokinetic results indicate a difference in the characteristics of the lithotypes. The isoelectric points of 4 anthracites and 12 lithotypes were obtained. It was suggested that the relative flotation rates of the lithotypes were pH dependent and that the maximum flotation rate of anthracite occurs in an acidic circuit. Although there has been an increased interest in the electrokinetic properties of coal,' research on the subject is still in an early stage of development."' To the authors' knowledge, no electrokinetic studies have been made on coal lithotypes, particularly anthracite litho-types. This paper presents the results of an investigation of the double layer properties displayed at the anthracite/water interface (whole coal and lithotypes) as determined by streaming potential methods. It is hoped that this investigation and related future investigations will provide correlations from which the surface properties of any coal can be predicted and then related to surface-dependent processes such as froth flotation and flocculation. Another aspect of this research, undertaken to determine the physical and chemical parameters necessary for anthracite lithotype differentiation, was previously published.? The number of parameters involved, lithologic, organic and inorganic, and the wide divergence of these parameters within an individual coal limits the practical utilization of the results; however, the result? are of value and of interest in guiding theoretical developments. Keeping the limitations in mind, the results are analyzed in terms of their application to froth flotation processes and are used to indicate the feasibility of making a lithotype separation by flotation. Experimental Procedure Prior to discussing the experimental work per se, it would be of value to establish an understanding of anthracite lithology. Anthracite Lithology: Coal seams display two different modes of variation, rank and type. A coal's position in the continuous series ranging from peats through anthracites determines its rank. The rank of the material under consideration is anthracite. The different bands of coal which constitute a coal seam are distinctly contrasted in regard to physical properties and chemical composition. These megascopic bands are the coal types and are termed lithotypes., A megascopic examination of 11 anthracites revealed three distinct, homogeneous, lithotypes. The classic description of bituminous coal lithotypes as proposed by Stope" was found to be quite adequate for recognizing the three lithotypes in anthracite, namely vitrain, durain, and fusain. The term vitrain describes the brilliant constituent of coal; durain describes dull coal; and fusain is the term applied to fossil charcoal. The anthracites studied were generally found to contain 60-80% vitrain, 10-30% durain, and 1-10% fusain. A complete description of the physical characteristics and chemical composition of the studied lithotypes can be found in a previous publication.' Sample Preparation: Nine of the anthracites used in the investigation were from Pennsylvania, one was from Russia, and one from Wales. Table 1 shows the various designations and sources of the employed anthracites. The letter V, D, or F added to the whole coal designation indicates respectively the vitrain, durain or fusain lithotype of that coal. The samples were carefully collected to avoid contamination. To insure against oxidation, the samples were obtained as fresh as possible and stored under nitrogen or water. Generally a representative sample of the seam and samples containing high concentrations of one or another of the petrographic constituents were secured for each coal. Pure lithotypes were prepared by manual separation and selection. The pure lithotypes and representative samples were ground to —35 mesh and screened to 35 x 48 mesh. The 35 x 48-mesh fraction was then passed over a magnet to remove iron contamination, washed with doubly

Jan 1, 1971

By P. Hazebroek, C. S. Mathews, E. E. Allen, H. C. Lefkovits

A rigorous study was made of the behavior of reservoirs composed of horizontal layers, unconnected except at the well and filled with a compressible fluid. The report is presented in two parts. Part I deals with the practical implications of the results obtained; Part 11 contains the mathematical derivation of the solution. The main portion of Part I is concerned with application of the results to reservoirs composed of two layers. Relative rates of depletion of the layers are studied, and it is shown that differential depletion between layers exists in the transient stage of the reservoir, which generally is of an order of magnitude longer than the transient stage in a single-layer reservoir. In the transient stage, the more permeable layer is depleted faster than the less permeable. However, the reservoir approaches a steady-state situation where both layers contribute equally to production. Theoretical build-up curves from such reservoirs are presented, and the influence of a skin effect and flow into casing and tubing are also evaluated. The build-up curves are predicted to have, first, the familiar logarithmic straight-line section and, subsequently, a rising and flattened section. The results found are compared with an extension of an approximate theory, and it is found that this simplified theory is applicable over most of the life of the reservoir. Extensions to reservoirs containing more than two layers are indicated, and examples of the performance and build-up curves for three-layered reservoirs are presented. The theoretical results on build-up curves were applied to field examples of such reservoirs, and satisfactory results were obtained. From the build-up curve, the pemeability-thickness product, the wellbore damage and the static pressure are obtained. However, it apparently is not possible to determine the properties of the individual layers from the combined build-up curve. A large number of reservoirs have been found where the producing formation is composed of two or more layers of differing physical characteristics, such as permeability and porosity, and where also the thicknesses of the layers differ. Since in general a differential depletion should exist between the layers of such reservoirs, it would be advantageous to know the amount of the differential depletion under a given production history. It also would be valuable to know the pressure behavior, because it could be undesirable to produce a reservoir in such a manner that the pressure in one of the layers would have fallen below the bubble point of the oil at a time when another layer might still be virtually undepleted. The determination of static pressures in shut-in wells with slow build-up is another feature of importance in layered reservoirs. If the behavior of the reservoir differs appreciably from the predicted behavior of a single-layer reservoir, the type of analysis for build-up curves suggested for single-layer reservoirs is not applicable. Several authors have treated the problem of finding the pressure and production characteristics of multilayer reservoirs. Horner treated the problem of n layers in an infinite field, the layers being connected only at the well. Tempelaar-Lietz2 has presented an approximate treatment of the characteristics of a bounded reservoir composed of two layers of different permeabilities and equal thicknesses. Homer gave no information on differential depletion between layers, and the treatment of Tempelaar-Lietz was not applicable for prediction of pressure build-up behavior. In addition, it was thought that a more rigorous treatment than the one by Tempelaar-Lietz would be valuable in determining the range of validity of this solution. The present study, therefore, was made of a bounded reservoir composed of two or more layers,

By G. Derge, R. E. Grace

A S detailed studies of mass transport in hetero- geneous systems are made, a knowledge of the chemical diffusion coefficients in various liquid and solid phases is necessary to understand the kinetics of any total reaction. For example, in zone refining some information must be available about the diffusion coefficients of various species in the liquid and solid regions near the moving interface. In liquid-liquid reactions, of which slag-metal reactions are of particular interest to metallurgists, the diffusion coefficient of a transferring species must be known accurately in both phases in order to predict a transfer coefficient for the over-all process. Diffusion data for various elements in liquid iron and iron-carbon alloys have been roughly deter-

Jan 1, 1959

Jan 1, 1915

By H. R. Peiffer

Composite alloys of silver and alumina are shown to resist flow above the melting point of the continuous matrix. The ability to resist flow depends on the fineness of the dispersion and the oxygen content of the silver. It is believed that the oxygen influences very strongly the bond between the molten silver and the finely divided alumina. RECENT needs for materials with high strength and creep resistance at high temperatures initiated mechanical property studies on dispersed phase materials to near the melting point of the continuous matrix material. Results' of these investigations have shown that certain of these materials do have promise for high-temperature applications. Experiments performed on composite materials of silver and alumina by the author have resulted in the discovery of an interesting effect above the melting point of the silver. In these materials the silver was continuous and the alumina very finely divided (Linde B). It was observed that these materials exhibited strength and resistance to flow above the melting point of the silver matrix. The purpose of this paper will be to describe these properties. METHOD OF PREPARATION The materials were prepared by mixing the proper amount of Linde B alumina and high-purity silver oxide. The alumina content was varied from 5 to 20 wt pct alumina in silver in 5 pct steps. The materials were mixed by blending the constituents in an ordinary food blendor using ethyl alcohol as a vehicle. Enough alcohol was added to the powders to form a mixture with the consistency of a thin mud. After blending for about | hr the material was dried and the silver oxide reduced by heating to 450 OC. The material was then pressed at 25 tsi into a -in. billets 3 in. long. EXPERIMENTAL PROCEDURE The specimens were horizontally supported at either end by knife edge supports of cold-rolled steel. This holder was then placed in a "globar" furnace and a chromel-alumel thermocouple placed very close to the specimen recorded its temperature to within 10°C. Each specimen was heated rapidly to 900°C initially. The specimens were held at temperature approximately 30 min and then the temperature was raised 50 deg. The procedure was repeated until deformation was noted. Photographs were made of the specimens at various temperatures and increments of time using a Polaroid Land camera. RESULTS Fig. 1 shows the 5 pct by weight "Linde B" alumina and silver material after reaching 980 °C. Failure occurred after 15 min at this temperature. There were two points of failure and silver collected at them. No additional flow of the molten silver was noted at any other place. Fig. 2 shows a 20 pct by weight "Linde B" alumina in silver specimen. After 30 min at 1400°C, bowing of this material was observed. Other concentrations of alumina were added to

Jan 1, 1961

Jan 1, 1893