Search Documents

By John J. Howard

WE are approaching the depletion of our principal source of iron ore-the Great Lakes deposits, which have provided 85% of the nation's requirements for the past fifty years. This situation presents a threat to our standard of living and our position as a world power. Fortunately, in the Great Lakes region there are still tremendous quantities of potential iron ore in the form of the low iron, high silica rock called taconite. The economical extraction of iron from taconite will insure our future steel supply if no new deposits available to the United States even in time of war are discovered. In the new process presented here, the iron is reduced directly by a simple method and then separated from the silica. The product is "feed," not to the blast furnace, but to the steel plant. This process requires very much less plant, less physical and chemical treatment, and less fuel and auxiliary materials than the conventional ore concentration-blast furnace method. In my opinion, this new, fundamentally different approach offers a better hope for the solution of the iron ore problem.

Jan 5, 1950

By B. P. Mulcahy

When the phrase "selection of coal for carbonization" is used, there is always the implied continuance of thought "to make good coke.'' The reason for this, of course, lies in the fact that, in almost all instances, when coal is carbonized coke is the principal product. Under certain conditions the yield of gas may also be a factor, but even here it must be secondary to the coke yield, for in every instance coke represents the largest single product of the process. The importance of coke to the byproduct industry has been considerably enhanced during the past 20 years because of the continuously decreasing financial returns of all the by-products. This fact will account, in part, for the rebirth of interest and investigation in the carbonization process during the past 10 years. Many papers have been written on this subject, with naturally divergent thoughts because of the diversity of interests, but in each instance the common aim was the same—the making of better coke. Scope of Investigation In perusing this literature, the writer was struck with the constantly recurring imposed condition of asking for better coke, but with the distinct unwillingness to make any concession to temperature of carbonization. When there is a high demand for coke, the only means by which the industry can increase the quantity is to shorten the coking time by an increase in temperature, or to increase the quantity of low-volatile coal, or both; and since in many instances the percentage of low-volatile coal can be increased only in small quantities, because of factors to be discussed later, the big increase must come from shortening the coking time. When this is done most of the improvement accomplished by the selection of the coals in the mixture is lost. It is not felt necessary in this paper to discuss the advantages of minimum ash and sulphur and other materials in coal. The value of minimum contents of these materials in coke is well established. When the use of coals high in these contents is dictated, the selection of coals, as we will consider it here, cannot apply to full advantage. The scope of this paper, then, will be to discuss the factors of inherent coal characteristics and operating procedures that influence coke quality, for they are fundamentally related and both must be considered if we are to attain our objective of better coke. A study of either must embrace a study of both simultaneously. To properly evaluate the influence of the coal and to help in the selection, we must first be able to appraise the coke, and interpret fairly the influence of the process in all of its aspects. Appraisal of Coke To refer simply to the quality of coke gives no indication of what is meant, for the term is too general in its implication. An analysis of a coke is divided usually

Jan 1, 1944

By B. P. Mulcahy

When the phrase "selection of coal for carbonization" is used, there is always the implied continuance of thought "to make good coke.'' The reason for this, of course, lies in the fact that, in almost all instances, when coal is carbonized coke is the principal product. Under certain conditions the yield of gas may also be a factor, but even here it must be secondary to the coke yield, for in every instance coke represents the largest single product of the process. The importance of coke to the byproduct industry has been considerably enhanced during the past 20 years because of the continuously decreasing financial returns of all the by-products. This fact will account, in part, for the rebirth of interest and investigation in the carbonization process during the past 10 years. Many papers have been written on this subject, with naturally divergent thoughts because of the diversity of interests, but in each instance the common aim was the same—the making of better coke. Scope of Investigation In perusing this literature, the writer was struck with the constantly recurring imposed condition of asking for better coke, but with the distinct unwillingness to make any concession to temperature of carbonization. When there is a high demand for coke, the only means by which the industry can increase the quantity is to shorten the coking time by an increase in temperature, or to increase the quantity of low-volatile coal, or both; and since in many instances the percentage of low-volatile coal can be increased only in small quantities, because of factors to be discussed later, the big increase must come from shortening the coking time. When this is done most of the improvement accomplished by the selection of the coals in the mixture is lost. It is not felt necessary in this paper to discuss the advantages of minimum ash and sulphur and other materials in coal. The value of minimum contents of these materials in coke is well established. When the use of coals high in these contents is dictated, the selection of coals, as we will consider it here, cannot apply to full advantage. The scope of this paper, then, will be to discuss the factors of inherent coal characteristics and operating procedures that influence coke quality, for they are fundamentally related and both must be considered if we are to attain our objective of better coke. A study of either must embrace a study of both simultaneously. To properly evaluate the influence of the coal and to help in the selection, we must first be able to appraise the coke, and interpret fairly the influence of the process in all of its aspects. Appraisal of Coke To refer simply to the quality of coke gives no indication of what is meant, for the term is too general in its implication. An analysis of a coke is divided usually

Jan 1, 1944

By J. W. Pugh, J. D. Nisbet

F. B. Foley—The use of data published by Wever and Jellinghaus in 1931 to fix boundaries of the sigma phase in the Fe-Cr system, in the face of the author's own references to the suggestions of Bradley and Goldschmidt, Aborn and Bain, and Hougardy that the phase is much more extensive, and the very much more accurate work, which weighs heavily in favor of these suggestions, of Cook and Jones, published in 1943 and evidently disregarded by the authors, makes their derived ternary diagram, especially fig. 15 for 400°C, quite inaccurate on the Fe-Cr side and affects the extent of phase boundaries in the most controversial and important part of this ternary system. In commercial Fe-Ni-Cr alloys the occurrence of sigma has been observed time and time again at lower chromium contents than that of the 24 pct Cr, 16 pct Ni, 60 pct Fe alloy which is the lowest permitted by fig. 15 of practically carbonless metal. Newel1 reports sigma in 27 pct Cr-Fe even with some carbon present to be one of the greatest detriments to its extensive application, whereas Pugh and Nisbet set a low limit of 36 pct Cr for sigma in the binary Fe-Cr system. J. J. Heger—The diagrams presented by the authors do not agree with observations made on commercial Fe-Cr and Fe-Cr-Ni alloys, nor do they agree with two recent investigations made on the Fe-Cr and the Fe-Cr-Fe systems. I refer first to the investigation made by Cook and Jones1' on the sigma region of the Fe-Cr system. On the basis of their results which were published in 1943, Cook and Jones established new boundary limits for the sigma and the alpha plus sigma regions. These new limits have been accepted and are incorporated in the Fe-Cr diagram that appears in the 1948 edition of the Metals Handbook. This diagram is shown here as fig. 34. As will be noted, the boundary limits of the alpha plus sigma region in this diagram extend to much lower chromium contents than do those in the diagram presented by the authors in fig. 2. These new limits indicate that sigma phase should form in an Fe-Cr alloy containing 26 pct Cr, and experience with commercial alloys confirms this finding. Indeed, recent studies on a commercial Fe-Cr alloy containing 17 pct Cr have shown sigma phase to be stable in this alloy at 550°C. I recognize that the authors' work did not include studies on the sigma region; however, I believe this is a serious omission because sigma phase may profoundly affect the physical properties of these alloys and should be evaluated in any investigation which attempts to relate physical properties to the equilibrium diagram. The second investigation to which I refer is that made on the Fe-Cr-Ni system by Rees, Burns, and Cook,'' who used pure alloys and employed heating 17 W. P. Rees, B. D. Burns, and A. 3. Cook: Journal Iron and Steel Institute. (July 1949) 162, Part 3. p. 325. times that extend to 200 days. These investigators published their results in July 1949 and from these results constructed isothermal sections at 800" and 650°C. The isothermal section at 650°C is shown here as fig. 35. This diagram indicates sigma phase should form in a pure 18 pct Cr-8 pct Ni alloy. Although sigma phase has not been observed after 10,000 hr at 1200°F in commercial 18-8 alloys containing carbon and nitrogen, it has been observed under the same conditions in 18-8 alloys modified with titanium and columbium, both of which serve to reduce the effect of carbon and nitrogen. This section and the one at 800°C suggest that the constant iron sections which are presented by the authors, should be considerably altered, if they are to represent an accurate picture of the system. A few of the suggested alterations are as follows: In fig. 9, the section at 50 pct Fe, the gamma plus sigma region should be widened, not narrowed at 800" and 650°C. In fig. 10, the section at 60 pct Fe, the gamma plus sigma region should be widened at 800° and 650°C. In fig. 11, the section at 70 pct Fe, an alpha plus sigma, an alpha plus gamma plus sigma, and a gamma plus sigma region should be added. In fig. 12, the section at 80 pct Fe, the alpha plus gamma region should be widened at 800°C. In fig. 13, the section at 90 pct Fe, the alpha plus gamma region should be widened at 650° and 800°C. Undoubtedly, the chief reason for the discrepancies between the authors' data and those of Rees, Burns, and Cook is that the authors did not employ long enough heating times to allow for transformation. In this connection, I wish to warn that transformations in these alloys, particularly transformations at temperatures below 800°C, are extremely sluggish and may require a year or more to approach completion. Therefore, unless extremely long heating times are employed or steps are taken to accelerate these transformations by such means as mechanical working, the results will not yield an accurate picture of the alloy system. Certainly, an accurate picture is needed for the development of better high-temperature materials. E. J. Dulis-The purpose of this work is not clear. If an improvement of the ternary equilibrium diagram of the Fe-Cr-Ni system was wanted, it seems logical that testing techniques superior to those previously used would be a prime requirement. To approach equilibrium in this system, long holding times are needed; a fact established long ago but apparently ignored by the present authors, who used the continuous heating and cooling tests in equilibrium studies. A publication on the same system by Bradley and Goldschmidt6 was criticized by Monypenny in a

Jan 1, 1951

By C. D. Wiseman

THE concept of alloying to increase the strength of metals originated during the bronze age. However, at the present time there is no single theory capable of explaining all of the observed strengthening effects of alloying elements on the mechanical properties. In general, it may be said that solid solutions are stronger than the pure metal and that the strengthening effect increases with increasing alloy content. Various theories for solution hardening have been proposed, the first of which was presented by Rosenhain who suggested that the alloying elements roughened the slip planes, thereby requiring a higher stress to initiate slip. Recent work by French and Hibbard2 confirmed Norbury's3 conclusion that those alloying elements which cause a greater change in lattice parameter have larger effects on hardness. However, a given change in lattice parameter produced by different alloying elements does not cause the same change in hardness. A further refinement was suggested by Dorn, Pietrokowski, and Tietz4 who considered differences in valence between the solute and solvent with the change in lattice parameter to explain the plastic properties of aluminum alloys. Allen, Schofield, and Tate5 further investigated the valency contribution to solution strengthening by testing some copper-base solid-solution alloys having constant electron densities. Tensile tests performed on these alloys gave identical stress-strain curves even though the atomic size effect, which varied by a factor of two, was neglected. The advent of dislocation theory6-8 provided a new and powerful tool capable of explaining many phenomena of plastic deformation and indicated new approaches to solution hardening. The basic con- cept of recent theories is that solution hardening is not due to stresses associated with randomly dispersed solute atoms, but rather to a nonuniform distribution of the solute. This conclusion was reached by consideration of the effective tension present on each dislocation line and the ability of a dislocation to pass an obstacle. cottrell suggested the possibility that the internal stresses due to randomly distributed solute atoms would offer essentially no resistance to the passage of dislocations. He reasoned that an edge dislocation may be considered as a rigid line discontinuity. As the dislocation moved through a crystal, the random stress fields would be equally distributed along its length. Since half of the stress fields would be acting to move the dislocation forward and the other half trying to move it back, the net effect on the dislocation would be zero. Thus the randomly distributed solute atoms would not contribute appreciably to solution strengthening. Mott and Nabarro10 considered the dislocation as a flexible, rather than a rigid, discontinuity. They obtained a simple model for a dislocation moving in a lattice having precipated particles, where the dislocation would actually bend around the obstacle until it would loop back onto itself to rejoin and then continue onward. Their work indicated that the minimum radius of curvature of the dislocation line, under the action of an external stress and in the region of an internal stress, would be such that the dislocation would be unable to pass through a matrix containing small closely spaced precipates by the looping process. The dislocations would tend to remain rather straight, approaching the condition of Cottrell's rigid dislocation. Hence, the strengthening must not be due to random solute atoms; however, it might be due to the concentration of atoms, either as clusters of like atoms or as short-range ordered regions, or to the concentration of solute atoms around dislocations. To date, four mechanisms of solution strength-

Jan 1, 1959

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

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

Jan 1, 1945

By B. Fazan, O. D. Sherby, J. E. Dorn

McLean's technique was employed to determine the effect of temperature on the contribution of grain boundary shearing to the total creep strain in pure aluminum over the range of 610° to 747°K. The contribution of grain boundary shearing at the same stress was found to depend upon a temperature-compensated time, where the activation energy AH was practically identical with that for total high temperature creep. SEVERAL outstanding investigations by McLeanl-' have demonstrated that the total creep strain in polycrystalline aluminum at 473°K arises from microscopically detectable slip, subgrain tilting, and grain boundary shearing. Whereas microscopically detectable slip arises from dislocations that move out of the grains, subgrain tilting is due to entrapment of dislocations of like sign in subgrain bound-arles. Consequently, creep in polycrystalline aggregates appears to be the resultant of two mechanisms, namely, migration of dislocations and grain boundary shearing. This suggests that an appropriate law for creep should contain two additive terms ?1 = ?d + ?yb where the total creep strain, ?1, depends on the sums of the creep strains arising from motion of dislocations, ?d, and from grain boundary shearing, ?yb. But extensive investigations5 over wide ranges of alloys, grain sizes, temperatures, and stresses have shown that the total creep strain is quite accurately dependent on the single term functional relationship ?1 = f (?), s = constant where s is the stress (constant),* ? = te-?H/RT, t is the time under stress, AH is the activation energy, R is gas constant, and T is absolute temperature. Since Eq. 2 was found to be valid over those ranges where appreciable grain boundary shearing is observed, it appears probable that the activation energy for grain boundary shearing might be identical with the activation energy for migration of dislocations. Thus, under a given stress, it could be thought that where fd and fgb represent the appropriate functions for each mechanism of creep. The primary objective of this investigation was to obtain a direct check on the accuracy of this hypothesis. Experimental Procedure and Results Rolled aluminum sheet (99.987 pct Al), 0.100 in. thick, was used in this investigation. Creep specimens having a 0.25 in. wide, 3 in. long gage section were so machined that their axes were in the rolling direction. All specimens were annealed for 9 hr at 894°K before testing to produce a mean grain diameter of about 0.1 in. One face of each specimen was polished electrolytically in 10 pct HBF4. In order to permit accurate measurements of grain boundary shearing, the polished surface was lightly scribed with a ruling machine accurate to ±0.0001 in. to give a uniform grid of lines which were 0.01 in. apart. Although it was thought that surface working might modify the creep behavior in the vicinity of the scribed grid lines, this technique nonetheless was employed because such local differences in creep properties should not modify seriously the fractions of the total creep strain due to grain boundary shearing or to migration of dislocations. All creep tests were conducted under constant load with an initial stress of 250 psi. The specimen tem-

Jan 1, 1955

By W. G. Fischer

Basic laboratory tests on trona and the surrounding shales initiated the Rock Mechanics program. The stress-strain curve, modulus of elasticity, Poisson's ratio, the uniaxial rock strength, Mohr's envelope, the biaxial stresses at failure, and creep were investigated. A series of underground problems were then approached using this information and various field measuring devices, most of which were developed by the Bureau of Mines. Initially, stress concentrations near mine openings were evaluated using the stress relief technique. This required an accurate determination of the pre-mining stress field. Later, stress concentrations associated with the cave line were studied. After about 30 stress reliefs over an appropriate time interval the effects of one type of mining could be compared against another. The microseismic technique was used to investi- gate a possible application of warning devices near the cave line. A study of mine reorientation was made. Problems related to the shape and size of pillars and barriers were studied. The effectiveness of roof bolting patterns was examined. Control of roof stresses was attempted. A new system of mining in heavy ground has been developed using the information secured in the Rock Mechanics program. Without this system, mining in more than one instance would have been next to impossible. Indeed, from this one discovery alone, the Rock Mechanics program has paid off in improved safety as well as in dollars. The Westvaco trona* mine is located near the town of Green River in the southwestern corner of Wyoming. It is owned and operated by FMC Corp. on land leased from the US Government, the State of Wyoming, and the Union Pacific Railroad. A conventional room and pillar system is being used, (Fig. 1) with complete removal of the pillars during final mining. Return air bleeders surround

Jan 1, 1964

By Clarence P. Linville

A previous article1 by the authors contained a general description of the new roasting furnace herein described but it did not go into detail as to the metallurgical behavior or the results obtained. Believing that such information would be of great value, they have elaborated on the subject and have given many unpublished details. The furnace described applies the principle of roasting finely divided zinc-sulfide ores, now produced in large quantity by the flotation process, in gaseous suspension; that is, the ore particles are carried, in suspension, in a current of air and gaseous products of the roast. The relatively great fineness of flotation concentrate presents difficulties and problems of roasting in furnaces of the ordinary type; the fine ore is forwarded through the furnace in the form of a shallow bed and its very fineness leads to dense impervious bedding which prevents oxygen from reaching the interior of the bed, thus unduly lengthening the time of roasting and preventing the elimination of the last of the sulfur. The fineness of the concentrate, normally, should lead to a rapid and complete roast, for the speed of roasting is a function of the surface exposed to oxygen, which surface is greatest, per unit of weight, in very fine material. The difficulty in bed roasting is to get the oxygen to the particle. If the fine ore, during the roasting, could be freely suspended in oxidizing gases, full advantage could be taken of the great surface conferred by its fineness. This fundamental idea, of course, is not new, for the Stedtefelt furnace, familiar to the older metallurgists, is an example of it; but the manner in which this is accomplished may be new. The numerous efforts to roast in gaseous suspension show that the idea is attractive; in fact, an analysis would indicate that it is the most reason-

Jan 1, 1925

By Henry F. Adams, Guy H. Ruggles

IN this paper the authors aim to chronicle the experience and salient points brought out in changing flotation reagents at a concentrator which had probably been using a mininium amount of oil at a minimum cost per ton, to a more complicated system requiring a partial chemical control. The original oils were coal tar and pine oil. The new reagents are lime, xanthate and pine oil. It was found that there were no insurmountable difficulties and eventually the cost of the new reagents per ton of ore proved to be very little more than that of the old. LIME PLANT When the question of handling lime came up there were two propositions open: (1) to handle the lime dry; (2) to handle it wet in the form of an emulsion. Granting that a dry lime feeder would function properly, delivering lime uniformly, the chief objection was the dust that would be raised when these feeders were being charged or operated, as the only possible location was on a gallery beneath which men were working. With this objection the handling of lime as an emulsion seemed to be the better scheme. The lime plant which was first installed was for experimental work on one section. This was gradually changed and developed until it was of sufficient size to accommodate 20 sections. The various changes will not be discussed and the following description deals only with the fully developed plant. Crude as it is, and perhaps somewhat expensive to operate, the lime-handling plant has been quite successful. Much has been learned which will pave the way for a better installation in the future. Burnt lime is received loose in standard gage box cars. This is the product of the kilns and has had no screening or sorting. A grab sample is taken from each car as it is unloaded. An average of the analyses of samples from 44 cars gave the following: [ ]

Jan 1, 1928

By J. F. Wolff

During the past 4 or 5 years, much has been added to the detailed geologic knowledge of the Mesabi Range. This has not been in the direction of discovery of any new fundamental facts, but of detailed study, subdivision and correlation of different parts of the whole formation and of individual orebodies. Prior to this time, mining engineers in the district were so engaged with the commercial interests of exploring and developing orebodies that close geologic study and subdivision were done in a few instances only. The demand for refinement of work in .this direction has led 'the engineers of the Oliver Iron Mining Co. to do extensive structural subdivision and correlation in all exploration work during the past 4 years. Such work has become a commercial necessity rather than a scientific refinement, and at the present time is being extended to all parts of the Range. In the summer of 1914, the author of this paper wrote a series of articles on the orebodies and special features of the Mesabi Rangc, which was published in the Engineering and Mining Journal, issues of July 17 to Aug. 7,1915. Since that time studies of subdivision of the iron-formation have been extended considerably. The principal feature of this paper is the presentation of the subdivisions of the iron-formation. To this is added a discussion of the relations of the orebodies to the gentle folding and fracturing of the formation, and special features of the Range. The outline will be as follows : I. General geology. 11. Subdivision of Biwabik iron-formation. 111. Relation of orebodies to folding and fracturing of the iron-formation. IV. Special features. Acknowledgnlent is due to W. J. Olcott, President, and John Uno Sebenius, General Mining Engineer, of the Oliver Iron Mining Co., for permission to use the information presented in this paper.

Jan 1, 1917

By C. Chiou, D. P. Seraphim

The effect of clustering on the superconducting properties of Al-Zn alloys has been studied by the ballistic induction techniques. The superconducting critical temperature, T,, changes when zinc-rich clusters are formed. The change in T, depends on the concentration and may be positive or negative, but always correlates with an effective decrease in the solute concentration of the alloy. Reversion after clustering effectively returns a 5 at. pct Zn alloy to the quenched state. These methods might be use&lly extended to the Al-Mg system, where X-ray data are difficult to obtain. In very dilute Al-Zn alloys, as in other tin,' indium, aluminum,2 or tantalums base solid solutions, there is a decrease in the superconducting critical temperature, Tc, roughly proportional to the temperature independent resistivity, i.e., -0.2°K per pS2cm. With increasing solute concentration, the T, generally reaches a minimum and then increases4 to a value well above that for the pure solvent. The change of T, with solute concentration follows an empirical formulation involving two constants which correlate with the scattering cross section of the impurities. As will be shown below, the Al-Zn alloys more concentrated than 1or2at. pct do not follow the empiricism, probably because they are unstable even when rapidly quenched.5 However, it seems possible to study at least the later stages of solute clustering by precise measurements of the 1', following various thermal treatments. A few experiments on quenched alloys, aged alloys, and tests on reversion are reported here. The heat treatments selected for obtaining the quenched and aged states were mainly deduced from the work of Dash and Fine.6 For the quenched state, specimens were homogenized at 480°C, quenched to -160°C, and immediately transferred and mounted in liquid nitrogen. Measurements on the superconducting properties and residual resistivities were then made at helium temperatures, after which the specimens were aged at room temperature for 3 to 5 hr, i.e., much longer than the time required for clustering to be essentially completed. The superconducting properties and residual resistivities were once again examined. To reach the reverted state of the A1-5at. pct Zn alloy, the aged specimen was heated for 5 min at 200°C and then tested as above.

Jan 1, 1963

By James Douglas

The development of the copper-resources of this country has kept close pace with the unfolding of its geographical area to commerce. In colonial days, when our English ancestors occupied only the Atlantic seaboard, insignificant quantities of copper were mined in Connecticut, New Jersey, and Pennsylvania, and the ore was shipped for treatment to England. The first steam pumping-equipment

Jan 1, 1891

By AIME AIME

MEXICO embraces one of the great metal and petroleum producing provinces of the world. In this respect its history dates back to the overthrow of the Aztec empire by a Spanish force under Hernando Cortes between 1519 and 1.521. Even before then, its richness in silver and other minerals was not unknown. But it was a treasure house for the Spanish conquerors until the country became independent in 1821. It has been computed that in the 400 years following 1521, Mexico yielded 1.55,000 metric tons of silver, worth $3,000,000,000, two-thirds of the entire world production. In 1935 the country accounted for 36 per cent of the world's silver output, 14 per cent of its antimony (in 1934), 13 per cent of its lead, 3 per cent of its zinc and copper, and 21/2 per cent of its petroleum. Contrary to the impression of some, its gold output is now comparatively small, though important in the past. Its oil, as well, formerly hulked much larger than now, in 1921 being one-fourth of the world output.

Jan 1, 1936

By C. G., Fink

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution.

Jan 1, 1950

By Joseph Kaye Wood

A metal is said to be overstrained when it is deformed beyond the elastic limit at a temperature well below the critical range, as in cold working. Quantitatively, overstrain might be considered as that part of the total elastic deformation of the piece of metal, left over after the external load is removed, that added to the permanent deformation due to plastic action will give the total permanent deformation. Ordinarily the effects of this phenomenon, which vary with the internal residual stress probably in accordance with Hooke's law, are more noticeable when the yield point of the metal is exceeded, but they probably also exist to a smaller degree when the load is just large enough to cause the least amount of permanent set. These effects, which we recognize as the result of overstrain, are as follows: 1. An apparent increase of the elastic limit in tension and a decrease of the elastic limit in compression, provided the external load is tensile. The reverse is true when the load is compressive. 2. An elastic after-effeet in which time and temperature are important factors. 3. A state of imperfect elasticity in which Hooke's straight line becomes slightly curved, giving rise to an hysteresis loop. 4. In addition to the apparent increase in the elastic limit, such properties as the hardness, ultimate strength, and resistance to fatigue failure are increased, provided the overstraining has not been carried far enough to make the metal brittle. 5. Correspondingly the ultimate elongation, reduction in area, magnetic quality, ratio of endurance limit (fatigue breaking stress) to elastic limit, and resistance to season cracking (in certain copper alloys) are decreased. The question naturally arises: how do these changes in the properties of a metal resulting from overstrain influence our method of design? The fact that most of the desirable qualities are increased makes overstraining a favorable process, from an engineering standpoint; but on the other hand, the loss of such qualities as perfect elasticity and complete

Jan 1, 1924

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit 'flash' chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om'nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.' One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.' By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By B. G. Klugh

(New York Meeting, February, 1913.) THE present paper represents a preliminary investigation of the ultimate structure of iron-bearing materials which have been subjected to heat treatment for the purpose of agglormer-ating the fines, or for chemical changes, or for both. Primarily, the object of this inquiry was to determine the relation of the microstructure of each of these materials-to its specific susceptibility to the action in the blast-furnace. It is hoped that this small contribution will serve as a nucleus to a line of research that will throw some light upon the debated questions involved in blast-roasting. Thus far the investigation has been conducted along lines of analogy of known principles, rather than through the applica-tion of any well-defined system of microscopic petrography. This is obviously due to the fact that we are dealing with materials which are the artificial products of a new art, rather than with the natural materials from which the essence of the pure science has been evolved. In the limited tune allowed for this research, it has been conducted upon those materials the chemical content of which allows of their use commercially in the blast-furnace.

Jan 5, 1913

By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.