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By C. Graeme-Barber, R. L. Bell, T. G. Langdon

An analysis is made of the formulas and ,methods used to estimate the contribution of grain boundary sliding to the overall strain of a polycrystal. The errors involved in the approximations and/or ,mistakes in earlier work are assessed quantitatively so as to make possible the critical use of previously published data. SINCE it has been found that, under conditions of very slow creep, the strain due to grain boundary sliding (?gb) may contribute as much as 80 pct of the total creep strain,1,2 it is obviously important to have reliable methods for estimating this grain boundary strain. In two recent papers Stevens3,4 has drawn attention to the pitfalls encountered in assessing ?gb. He criticizes 1) the assumptions made in the derivation of some of the formulas for ?gb, and 2) the indiscriminate averaging procedures used for obtaining the quantities substituted in these formulas. These and further criticisms of earlier work are mostly valid. Unfortunately the only formulas and procedures recommended are either impossible or very difficult to apply in practice. Furthermore no attempt is made to assess the errors involved by the earlier approximations or mistakes, and so it is not possible to make critical use of any of these early dab. The present article attempts to improve on these shortcomings by reference to empirical verification of easily applied formulas whose theoretical derivations involve some otherwise unjustifiable assumptions, and by a quantitative assessment of the errors in previous work. DEFINITIONS First it is necessary to define the terms and symbols to be used. The choice of symbols preferred here is a logical combination and extension of the v introduced by McLean5 and the u by Brunner and rant.' In Fig. 1 the two grains X and Y are displaced by the sliding vector AC. u is the component of sliding resolved along the stress axis, v is that measured perpendicular both to the stress axis and to the specimen surface, and w is that measured perpendicular to the stress axis but in the plane of the surface. Two angles define the orientation of the grain boundary: 8, between the stress axis and the surface trace of the boundary, and +, the internal angle on a longitudinal section cut perpendicular to the surface. In computing the strain resulting from the boundary displacement at all the in- dividual boundaries in a polycrystal the components u, v, or w are sometimes averaged along a longitudinal line (i.e., parallel to the stress axis), sometimes along a transverse line, and sometimes at randomly chosen boundaries. Averages obtained in these three ways are given subscripts 1, t, and r, respectively. Stevens rightly calls attention to the possibility of non-equiaxed grain shapes either at the start or at the end of deformation. In this article all values of numbers of grains per unit length will refer to measurements made before deformation. The subscripts 1 and t will be used for the number of grains per unit length obtained along longitudinal and transverse lines, r for that obtained by averaging along a number of randomly directed lines. FORMULAS FOR ?gb ?gt, as a Function of u. An obvious truth is that cgb can, in principle, be obtained by summation of all the v components at the boundaries intersected by a longitudinal line of known length I, viz.: where nl is the number of grains per unit length, parallel to the stress axis, in the unstrained specimen. There are assumptions in the analytic derivation of Eq. [I] due to Brunner and rant' but ~achinger' arrived at Eq. [la] by a rigorous method. Unfortunately the experimental procedure required by Eq. [ la] proves very difficult as boundary migration tends to obscure the points at which the longitudinal line meets the grain boundary and the errors on such measurements tend to be large, see Fig. 2. For example, on a specimen of Magnox AL 80 at a creep strain of 9.7 pct, 300 measurements of u obtained from the points of intersection of a longitudinal line with the grain boundaries gave ul = 8.95 ± 3.58 pm, or an error of ±40 pct, at the 95 pct confidence limit. These large errors due to migration may be avoided by measuring u from the separation of the segments

Jan 1, 1968

By Donald D. Smythe

This paper describes briefly the topography and geology of the region where the mica-bearing pegmatites are found and discusses prospecting, the quality of the mica, its preparation, and evaluation of the deposits. Muscovite mica occurs in a number of widely separated localities in Brazil, but production has come largely from deposits in the southeastern and eastern part of the State of Minas Gerais (Fig. I). There the deposits form a discontinuous zone, which starts at a point go km. north of the city of Rio de Janeiro and extends north for some 500 km., roughly parallel to the coast. A maximum width of 180 km. is reached along the Rio Doce. To the west in Minas Gerais, and extending east into the states of Espirito Santo and Rio de Janeiro, the mica zone proper is fringed by areas in which there are scattered occurrences of mica-bearing pegmatites. A few of these outlying deposits have produced commercial mica, but most of them are unimportant. To the southwest, in the State of Sao Paulo, there are a number of mines, which at one time produced a very considerable amount of sheet mica, largely as a byproduct of kaolin mining. These deposits, and a few others lying between them and the main productive areas to the northeast, appear to be the southwestern continuation of the strong Minas Gerais mica zone. In the vicinity of Conquista, just north of the Minas Gerais boundary in the State of Bahia, and still farther north, near Jacobina, there are several known mica deposits. Their location indicates that they may be the northern continuation of the main mica zone. The major part of Brazilian mica production has come from four areas within the mica zone proper; from north to south, Governador Valadares, Raul Soares, Espera Feliz, and Muriaé.. The first is go km. from north to south and reaches a maximum width of 180 km. The Raul Soares area extends 135 km. from northeast to southwest, and in places is 80 km. wide. The Espera Feliz area is 100 km. from north to south, and reaches a width of 35 km. The Muriai. area extends 150 km. from northeast to southwest and its width reaches 40 kilometers. Between the known productive areas, and in the areas directly to the southwest and to the north of them, little mica has been produced. These gaps, as well as certain irregularities in the outline of the mica zone itself, are to be ascribed either to lack of prospecting or to conditions preventing the discovery of mica, rather than to its nonexistence. Elsewhere in Brazil mica has been reported from eastern Goiaz, Ceará, Pernambuco, Rio Grande do Sul, Matto Grosso, and Amazonas. Production from these sources is negligible at present. Because of the inferior quality of the mica from the more accessible of these localities, and the operational difficulties occasioned by the remoteness of others, it is improbable that they will become important producers for some time to come.

Jan 1, 1948

By Donald D. Smythe

This paper describes briefly the topography and geology of the region where the mica-bearing pegmatites are found and discusses prospecting, the quality of the mica, its preparation, and evaluation of the deposits. Muscovite mica occurs in a number of widely separated localities in Brazil, but production has come largely from deposits in the southeastern and eastern part of the State of Minas Gerais (Fig. I). There the deposits form a discontinuous zone, which starts at a point go km. north of the city of Rio de Janeiro and extends north for some 500 km., roughly parallel to the coast. A maximum width of 180 km. is reached along the Rio Doce. To the west in Minas Gerais, and extending east into the states of Espirito Santo and Rio de Janeiro, the mica zone proper is fringed by areas in which there are scattered occurrences of mica-bearing pegmatites. A few of these outlying deposits have produced commercial mica, but most of them are unimportant. To the southwest, in the State of Sao Paulo, there are a number of mines, which at one time produced a very considerable amount of sheet mica, largely as a byproduct of kaolin mining. These deposits, and a few others lying between them and the main productive areas to the northeast, appear to be the southwestern continuation of the strong Minas Gerais mica zone. In the vicinity of Conquista, just north of the Minas Gerais boundary in the State of Bahia, and still farther north, near Jacobina, there are several known mica deposits. Their location indicates that they may be the northern continuation of the main mica zone. The major part of Brazilian mica production has come from four areas within the mica zone proper; from north to south, Governador Valadares, Raul Soares, Espera Feliz, and Muriaé.. The first is go km. from north to south and reaches a maximum width of 180 km. The Raul Soares area extends 135 km. from northeast to southwest, and in places is 80 km. wide. The Espera Feliz area is 100 km. from north to south, and reaches a width of 35 km. The Muriai. area extends 150 km. from northeast to southwest and its width reaches 40 kilometers. Between the known productive areas, and in the areas directly to the southwest and to the north of them, little mica has been produced. These gaps, as well as certain irregularities in the outline of the mica zone itself, are to be ascribed either to lack of prospecting or to conditions preventing the discovery of mica, rather than to its nonexistence. Elsewhere in Brazil mica has been reported from eastern Goiaz, Ceará, Pernambuco, Rio Grande do Sul, Matto Grosso, and Amazonas. Production from these sources is negligible at present. Because of the inferior quality of the mica from the more accessible of these localities, and the operational difficulties occasioned by the remoteness of others, it is improbable that they will become important producers for some time to come.

Jan 1, 1948

By Helmut Thielsch

IN recent years an ever increasing amount of interest has been directed toward research studying the principles and various applications of sonic and supersonic waves. Though still in their early stages of practical development, sonic vibrations are already used in the emulsification and degasification of liquids. Metals exposed to sonic or ultrasonic vibrations while solidifying show a considerable amount of grain refinement. Often sound waves are applied instead of radiography to test engineering materials for internal cracks and flaws.1 In the field of pure research these waves are used in dispersion and also in coagulation of particles or liquids in gaseous or, under certain conditions, in other liquid systems. In the settling and thickening of slurries considerable time is necessary to compress the solid particles and to squeeze out the liquid to obtain as low a dilution (liquid to solid ratio) as possible. Various methods have been developed to increase the amount of coagulation of the very fine solids (colloidal or semicolloidal) and to shorten the over-all time. The addition of small amounts of electrolytes and the warming of the suspension represent merely the more important techniques. Some of the effects of supersonic vibrations have been reported previously.2,6 From preliminary studies, therefore, it was hoped that by application of sonic vibrations it would be possible to reduce the time required to thicken such materials to a specific dilution, as well as to thicken to lower ultimate dilutions than could be obtained by quiescent settling alone. By increasing the volume thickened per unit time-i.e., improving the plant efficiency-great savings in equipment and time would be obtained for industrial processes. Also, faster settling rates should result if coagulation of particles could be increased. Experiments have been conducted for a period of several months in the Allis-Chalmers laboratory to study the effect of sonic vibrations on settling of particles of different sizes and concentrations. APPARATUS The sedimentation apparatus used in these experiments is illustrated in Figs. I and 2. The essential features are the stationary field coil and the movable voice coil. Both windings are placed around a solid iron core. A leather diaphragm connected to the steel frame holds the voice coil in place. A brass rod is fastened to the voice coil with a metal disk connected to the other end. This disk is sealed to the lucite cylinder with a flexible rubber diaphragm. The lucite tube is 17 in. long; its inner diameter is 2 ½in. and the wall thickness is ¼ in. The tube is calibrated on the outside in 10 c.c. divisions for a total of 1000 cubic centimeters.

Jan 1, 1946

By John D. Morgan

Uncertain world conditions of the present time require that this country be prepared to meet: 1) all out nuclear war with attack on the U. S.; 2) limited wars; 3) political, economic, and/or pyschological warfare. Our present position as a major world power derives in large measure from our free institutions and great industrial productivity, and this productivity in turn depends on a continuing flow of raw materials-metals, minerals, fuels, and agricultural products. The U. S., with only about 6 pct of the world's population, uses from one to two thirds of the world's annual supplies of most metals and minerals. The U. S. strategic materials stockpiling program is designed to enhance our national security position: as stated in the preamble of the Stock Piling Act, to decrease and prevent wherever possible a dangerous and costly dependence upon foreign nations for supplies of strategic and critical materials in times of national emergency.

Jan 8, 1960

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

By J. F. Haseman, J. E. Davenport

IN the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1-2 results in inadequate beneficiation. INVESTIGATION OF FLOTATION METHODS Flotation has been used in Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate.3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over-all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P205 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P205, 20; Si02, 40; CaO, 29; Fe203, 2; A1203, 3; F, 2.3. The particle-

Jan 1, 1947

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By H. A. Schwartz

FROM time to time, one of the authors has had occasion to investigate the graphitizing reaction and has published the results mainly as discussion1 of the work of other investigators. In view, therefore, of the diversity of both observations and interpretation, it seemed well to attempt a revision of the entire subject in the Research Laboratory of the National Malleable Castings Co. The work consisted of a careful study of a single, impure, iron-carbon alloy. The material, which may be considered typical low-carbon white cast iron of the malleable industry, was an air-furnace iron of the following composition: carbon 2.30 per cent., silicon 1.20 per cent., manganese 0.29 per cent., phosphorus 0.156 per cent., sulfur 0.048 per cent. The freezing range extended from 1213° to 1132° C., the latter figure agreeing with Gontermann's data .2 We have attempted to define the equilibrium diagram of this alloy, in the stable condition as related to the metastable diagram, from a temperature somewhat below the eutectic freezing point to a temperature below Ar1 and for a graphitic-carbon content from practically nothing to the original total carbon of the specimen (see Fig. 6). More especially we desired to locate the line in the stable diagram corresponding to the Acm line of the metastable system, which is designated by analogy, the Atm line (tm from temper carbon) ; also to determine the location of Aim with respect to Acm toward their lower extremities at Ar1 in order to determine whether or not graphitization is completed by the separation of an iron-carbon eutectoid analagous to pearlite in the iron-cementite system. This would involve further a comparison of the locations of the stable and metastable A1 points.

Jan 8, 1922

By Peter K. Strangway

During 1973, a 20,000 net ton (18 100 metric ton) formcoke test was carried out at Inland's 26.5-foot (8.08-meter) hearth diameter on NO. 5 Blast Furnace. The formcoke briquettes were produced from Elko1 coal by FMC at their pilot plant in Kemmerer, Wyoming. The briquettes were shipped to Inland in open railroad cars and most of them were placed in an outside storage field until a sufficient amount was available for the actual blast furnace test. The test consisted of three phases: an initial four-week base period; the actual 33-day formcoke test period; and a final three-week post-test base period. During the formcoke test period, the regular coke skip loads were gradually replaced with skips of formcoke until, after a three-week period, the replacement ratio reached 80%. The furnace operated smoothly and quality hot metal was produced. The burden remained permeable and it was possible to maintain wind rates 9 of over 100,000 scfm (47 Nm3/s) without significant blast pressure increases. Dusting from the formcoke was not a problem either in the stockhouse or in the top gas. The formcoke briquettes maintained their original shape and density as they descended through the furnace. When the 80 percent replacement level had been reached, the inwall temperatures became higher than normal (about 2000 ºF (1090 ºC)) and followed an unusual steady pattern. In addition, the top gas temperature became higher than normal, and the hot metal analyses and temperatures began to fluctuate unacceptably. In general, it is felt that the high inwall temperatures were a result of channeling of the hot furnace gases along the stack walls. This channeling appears to have been promoted by a change in distribution of the burden in the top of the furnace which, undoubtedly, was caused by the increased increments of formcoke. Since it was felt to be unsafe to operate the furnace for an extended period of time with the inwall temperatures at the high level, a decision was made to remove the formcoke from the furnace. When this was done, the inwall temperatures returned to normal. Once the inwall temperatures had returned to normal, the remaining 3,800 net tons (3450 metric tons) of formcoke were used in the furnace at a nominal 40% replacement level for five continuous days. The furnace operated smoothly during this period, and the results were representative of satisfactory furnace operation with partial replacement of regular coke with formcoke. The test was successful in proving that formcoke can replace up to about 50% of the regular coke in a large furnace operating at high wind rates. However, additional work will be required to develop acceptable charging practices for using higher levels of formcoke replacement.

Jan 1, 1977

By H. H. Campbell

The following paper deals almost exclusively with the results of practice at the works of the Pennsylvania Steel Company at Steelton, Pa. From the records of the furnaces at this plant, both acid and basic, large and small, are drawn the data for the various demon strations, and on a long and intimate experience with their opera tions are founded many theories and generalizations. It may seem that universal laws should not be built upon a basis so restricted ; but in reality the condition is the strongest guarantee of validity. Each table investigates some- certain variable, and by virtue of the common origin of the factors, we have good ground for assuming the corresponding agents to be equal. The examples may or may not be instances of good practice, and may be open to criticism if regarded solely as exponents of • metallurgical success. But it must be remembered that the lists are not made up of selected specimens, nor are they chosen to show su perior results; they are gathered to investigate, by strict scientific methods, the formula? of the operation. In such work no untoward results should be eliminated, save those which bear upon their face the stamp of experimental error. If the worst members be omitted, then the best must also be omitted. Only by using every available case can an honest attempt be made to deduce a true average. It is recog nized, however, that with the most careful selection it is difficult, if not impossible, to collect data representing universal conditions. In each table the records tell of a special practice, and all conclusions drawn from them are true only within the limits between which the equations have been integrated. Not assuming the prerogative of speaking for American melters in all the opinions herein expressed, nor acting as a camera in por traying an ephemeral state of national metallurgical development,

Jan 1, 1894

By Paul E. Rosten

Introduction This papers describes some of the latest improvements that have been incorporated or planned by the Cleveland-Cliffs Iron Co. to reduce operating costs and improve pellet quality. The Cleveland-Cliffs Iron Co. operates and manages mining, beneficiation, and pelletizing operations in Michigan, Canada, and western Australia. This paper deals with the grate-kiln pelletizing operations at Republic, Humboldt, Tilden, Empire, and Pioneer in Michigan, and the Adams and Sherman in Ontario, Canada. Table I characterizes each operation in regard to location, ore type, pellet capacity and date that pellets were first produced. All of the operations with the exception of Pioneer and Tilden, utilize downdraft-two-pass grate cycles of drying followed by preheating. Pioneer utilizes an all-downdraft, three-pass grate cycle which consists of three drying zones followed by the preheat zone. The Pioneer and Tilden cycles have been described previously (Lindroos and Koski, 1966; Villar and Dawe, 1975; Koski, 1977). Tilden utilizes a three-pass grate cycle with a stage of updraft drying, followed by two downdraft drying stages. Recuperation systems which supply hot gases to a drying zone from second stage cooling were designed and fur¬nished for Tilden I. Tilden II will be identical. Empire IV will also be furnished with a recuperation system. The Adams grate¬kiln system was retrofitted with a recuperation system. This paper will summarize some of the efforts that are in effect or planned for grate-kiln pelletizing systems to: (1) reduce operating and maintenance costs, (2) reduce energy requirements, (3) improve product quality, and (4) meet environmental standards.

Jan 1, 1981

By Arthur F. Taggart

Some years ago, A. M. Gaudin and one of the authors published a paper showing removal of tar acids from solution by sulfides preferentially as compared to gangues (specifically by galena as compared to quartz).' The underlying phenomenon was classed as adsorption, and the paper went on to develop the general thesis that so far as water-soluble frothing and collecting agents in flotation are concerned, the phenomenon of adsorption is one of controlling importance. Adsorption was defined in that paper as "a process of rearrangement of a system, which results in establishing a difference in concentration, as between the interfacial layers and the bulk of the phases, of a substance or substances initially uniformly dispersed in one or several of the phases." The paper went on to develop the relation between adsorption and surface cnergy according to Gibbs' equation (which may be thrown into the form U/c = KdT/dc, where U = excess concentration in surface layer, c = concentration, T = surface tension, and K is a constant), and pointed out that, according to this equation, degree of adsorption and change in surface tension vary directly. The present paper offers a somewhat different definition for the term adsorption; and sets up, in sweeping terms, the generalization that simple chemical reaction underlies the functioning of the flotation reagents which control mineral collection, when these reagents are soluble in and act from solution in the water of the pulp. Adsorption According to the modified definition, adsorption means concentration at an interface between different phases in a heterogeneous system (thus far the definition runs as before), by the action of some mechanism, of which nothing is properly implied in the word, and concerning which the user of the word is probably in entire ignorance. Thus defined,

Jan 1, 1930

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By Charles H. White

METHODS in colorimetry are based on the assumption that the intensity of the color of a definite volume of solution is directly proportional to the quantity of the color-producing substance' present. In the preparation and examination of colored solutions there are three ways in which the depth of color may be varied. These variables are; (1) the quantity of the coloring matter, (2) the quantity of the solvent, or the dilution, and (3) the thickness or depth of that portion of the solution examined. With these three variables as a basis, three general methods in colorimetry have been devised, all of which have been used in the determination of carbon in steel. In the first method, the quantity of the solution is kept the same for both the unknown steel and the standard, and the sections compared are of equal thickness, while the quantity of the standard is varied until the color obtained is of the same intensity as that produced by a definite quantity of the unknown steel. In laboratories where this method is used there is pre¬pared and kept for permanent use a series of solutions with varying amounts of the standard, representing the percentages of carbon from the lowest to the highest demanded in that laboratory. These standard solutions are kept in bottles, or test-tubes of equal diameter, and are arranged in series from the faintest to the most intense color, so that it is a simple matter to find the place of the unknown steel in the series, when the solution is of a definite volume and is contained in a tube of the same diameter as the standard tubes. In the second method, equal quantities of the standard and of the unknown steel are dissolved, the standard is diluted to a definite volume, and the solution of the unknown steel is di-

Sep 1, 1906

By R. I. Jaffee, F. C. Holden, H. R. Ogden

ECENT papers dealing with the properties of unalloyed iodide titanium have been directed primarily at the determination of base-line properties for alloy investigations. Early work was limited to a few tests because of the limited availability of iodide titanium at the time. In the results of papers by Campbell et al.,1 Gonser and Litton,2 Jaffee and Campbell,3 inlay and Snyder,4 and Jaffee, Ogden, and Maykuth, data on mechanical properties are presented for unalloyed iodide titanium in the annealed and cold-worked conditions. Data are presented in this paper which show the effects of heat treatment on the structure and mechanical properties of commercially produced iodide titanium. Correlation is made between microstruc-tural variables and the mechanical properties. Experimental Procedures Melting Stock: The melting stock used was as-deposited iodide titanium, produced by New Jersey Zinc Co. The furnished analysis showed the following range of impurities: N, 0.004 to 0.008 pct; Mn, 0.005 to 0.013; Fe, 0.0035 to 0.025; Al, 0.013 to 0.015; Mo, 0.0015; Pb, 0.0045 to 0.0065; Cu, 0.0015 to 0.002; Sn, 0.001 to 0.01; Mg, 0.0015 to 0.002; and Ni, 0.003. Hydrogen content as determined by vacuum-fusion analysis was 0.0091 wt pct (0.44 atomic pct) after arc melting and fabrication. Nitrogen analysis on the arc-melted and fabricated titanium showed a content of less than 0.002 pct N. The average hardness of the furnished stock was Rf 70, or approximately 85 VHN. Melting Procedure: The as-deposited rods were rolled, sheared, and degreased in preparation for arc melting. The charge was arc-melted with a tungsten electrode in a water-cooled copper crucible under a positive pressure of high purity (99.96 pct) argon. The final ingot was approximately 2 in. in diameter and showed no increase in hardness over that of the initial stock. Fabrication: Heating for fabrication was done in air. It was begun by forging the ingot into a 3/4 in. diam rod, at an initial temperature of 1600°F. Scale was removed by sandblasting. The rod was then swaged to 1/4 in. diam at room temperature through a series of 20 dies, with approximately 10 pct reduction in area between each die. An anneal of 1 hr at 850 °C in air was given after the 1/2 in. die, such that the final cold reduction was 75 pct. Sections cut from this rod were used for test and microstructure specimens. Heat Treatment: Heat treatments were carried out in resistance tube furnaces with stainless-steel linings, under an atmosphere of gettered argon. As further protection against contamination, the specimens were packed in titanium turnings in a titanium sleeve. Control experiments have shown negligible hardness increases with this method, indicating that contamination from oxygen and nitrogen is slight. Three cooling rates were employed in this work; these have been designated as water quenching, argon cooling (to simulate air cooling under a controlled atmosphere), and furnace cooling. The cooling rate for an argon cool is 100°C per min for the first minute, with an average cooling rate of 35°C per min over a 15-min period. A furnace cool requires about 10 hr, with an average cooling rate of 3.6oC per min during the first hour, and an average cooling rate of 1.2°C per min over the 10-hr period. Microimpact Test: The specimen adopted was based on the cylindrical Izod Type Y specimen (ASTM, E23-41T). All dimensions were reduced to half scale, including the notch radius. Specifications are shown in Fig. 1. The specimen is held vertically in an adapter and broken as a cantilever beam. Impact tests were run on a constant-velocity (11.34 ft per sec) Tinius Olsen impact testing machine with a total available energy of 100 in.-lb. Tests were made to determine the correlation between this microimpact and the standard V-notch Charpy impact test. Curves showing impact energy as a function of temperature for both impact tests are plotted in Fig. 2. Transition temperatures, when they occur, are about the same for both impact tests. All three titanium-rich materials have the same conversion factor, 10. Tensile Testing: Tensile tests were conducted on Baldwin-Southwark testing machines using the 600, 2400, or 3000 1b range. Specifications for the test specimen were taken from the 1948 edition of the ASM Metals Handbook, and are shown in Fig. 1. Strain measurements were made using an SR-4 resistance gage (Type A-7) cemented to the reduced section in conjunction with a lever-type extenso-meter. Readings on the SR-4 strain indicator were

Jan 1, 1954

By C. A. LINDBERG

Several new methods have been developed on the Iron Range to remove the material adhering to truck bodies in freezing weather. A machine known as a Gradall, incorporating the features of digging both above and below the horizontal, digging angle of blade control, full revolving, travel almost anywhere, and operated by one man, has proven successful in trials at body cleaning. Several of these units are in use with great saving in box-cleaning costs and improvements in efficiency of the truck operation with full capacity boxes. In addition to their winter use, the same machines have been used for ditching and excavating in the summer with great saving. The latest method of combating this freezing problem is to carry the exhaust from the engine through the body, making use of the tremendous heat that is now being wasted. To do this, the present wood sandwich which is used between the bottom of the box and the wear plate is removed and replaced with angles or channels run lengthwise of the box and spaced to permit gases to flow between or through them and also provide a good sup- port for the wear plate. The channels or angles are cut a little short on each end to form a cross passage that permits the gases to flow through the area. In the front end, openings are made in the wear plate and connect to a manifold created by welding a plate across the whole front of the box, spaced from the original end by the original vertical reinforcing angles at that point. The body being described is for a Euclid truck which is the only truck that has been adapted to this body-heating idea to date. At the rear of the truck, the holes from the cross passage are made in the bottom plate of the body and lead into a triangular-shaped body cross member under the scoop end of the truck.

Jan 1, 1949

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By E. L. Tucker

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

Jan 8, 1925