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By G. E. Johnson

The problem of efficient reclamation of zinc base die cast scrap became interesting early in 1930. Die Cast Metal, as referred to in this paper, is a zinc base alloy with various proportions of aluminum, copper, magnesium, antimony and tin. Many attempts were made to work out some means of reclaiming the discarded die cast metal for re-use as new die cast metal. Difficulties in such reclamation were attributable to contamination by lead and tin from solder, chromium and nickel from electroplated coatings, and iron from iron inserts. This paper relates the experiments that led to the development of a specialized muffle furnace for the treatment of zinc base die cast scrap for the production of zinc oxide and zinc, and describes the development of the muffle furnace and the equipment now used commercially for these purposes. The Eagle-Picher Co. acquired all patent rights' for these developments from the International Smelting and Refining Co. in connection with their purchase of the East Chicago Plant. Zinc Base Serap Situation About 1935, the die cast scrap situation became increasingly acute for scrap dealers. This scrap was accumulating from dismantling automobiles and household appliances which contained die cast parts. Efforts to find an outlet for this type of scrap were intensified. The International Smelting and Refining Co. began to study the possibilities of a commercial process for the recovery of values from die cast scrap. At that time most of the die cast metal reclaimed was melted down in small kettles of from one to five tons capacity, the iron inserts being removed by skimming. The dross was skimmed off and disposed of as a zinc dross. The drossed metal was cast into slabs and was given the trade name "die cast slabs.". Distribution of the products produced by melting die cast scrap in kettles is shown in Table 1. American Process Experiments A method considered for the production of zinc oxide from die cast scrap was an adaption of the standard American Process of zinc oxide manufacture. Thus some die cast scrap was mixed with oxidized zinc materials and charged to Wetherill grates. The zinc oxidized to zinc oxide but, while the aluminum and copper largely remained in the residue, the color of the zinc oxide produced was impaired by copper contamination. As the proportion of die cast scrap was increased, liquation took place; that is, the metal trickled through the charge then solidified in the openings of the grates. French Process Experiments Several hundred tons of die cast scrap were purchased for test purposes and converted into die cast slabs. These slabs were charged into a French Process (horizontal retort) zinc oxide furnace with some electrolytic zinc. A satisfactory grade of zinc oxide was not produced. Distillation in Belgian Retorts It was then decided that, rather than attempt to use scrap die cast metal or scrap zinc for the production of zinc oxide, it would be advisable to redistill the die cast slab metal in a Belgian retort furnace. The opportunity to do so was provided by the closing of the zinc smelter of the Illinois Zinc Co. at Peru, Ill. Arrangements were made for the operation of a Belgian retort furnace for such redistillation purposes. The results of this experiment are summarized in Table 2.

Jan 1, 1950

By R. W. Freeman, L. L. Tavlarides

The experimental methods used in obtaining kinetic data for solvent extraction systems can affect the validity of the results The method of contacting the two liquids should allow for accurate determination of the surface area, hydrodynamics, and diffusional processes The appropriateness of the Liquid Jet Recycle Reactor is discussed and the modelling of the mass transfer and chelation reaction is presented The LJRR is used to investigate the chelation of copper by LIX65N in toluene from aqueous copper sulfate sulfuric acid solutions The ranges of experimental variables are Copper, 1 8-13.8 g-dm-3, sulfuric acid 0-1.6 g-dm-3, LIX65N, 0 1-1.0 mol-dm-3 Data on the initial rate of copper chelation at the interface is generated Nonlinear regression analysis shows that the following expression adequately describes the data within experimental error.

Jan 1, 1981

By Robert J. De Angelis, James H. Barker

An improved method for solving dynawzical dislocation problems using a digital computer is described in this paper. Interactions between two distinct types of dislocations were studied: attractive screw dislocations; and Lomer lock forming dislocations. One dislocation is positioned in the lattice and is initially at rest, while the other dislocation is moved through the lattice on an intersecting slip plane at a constant velocity in the range 0.5 to 0.999C. (C is the transverse velocity of sound.) The results obtained from these computations indicate that screw dislocations account for a small fraction of the total strain over a wide portion of the range of velocities studied. They further indicate that mixed dislocations mainly repel other dislocations in the neighborhood of the active glide plane. From this a possible explanation for cell formation is put forth. The density of Lomer locks expected to exist after a strain of 0.2 was found to be 1.4 x 106 cm-2 which is in good agreement with indirect experimental estimates. IN the past, predictions of favorable or nonfavorable dislocation reactions were based on the associated changes in elastic strain energy. Such considerations take no account of the probability of the two dislocations coming into contact to react. Venables1 was the first to approach these probabilities by considering the interactions between two moving screw dislocations on perpendicular glide planes. Because of the restrictive types of dislocations and glide plane geometry employed, his results have limited application to metallic crystals. The work to be presented here develops a general approach to solving dynamical dislocation problems; either dislocation-dislocation interactions, presented here in detail, or dislocation interactions with any other suitably defined stress field. Two types of dislocation-dislocation interactions common to face centered cubic (fee) materials are considered: those between pure screw dislocations of opposite sign on intersecting slip planes and those between mixed dislocations on intersecting slip planes, that can react to form a perfect dislocation. This latter reaction, referred to as the Lomer reaction, produces a locked product dislocation that finds it energitical favorable to disassociate into two Shockley partials and a stair-rod dislocation. This partial configuration known as a Lomer-Cottrell (L-C) lock plays a major role in work hardening of fee crystals. seeger2 names the L-C lock as the prime contributor to Stage II hardening while Kuhlmann-wilsdorf3 and Meakin and Wils- dorf4 also state that it is a significant contributor to work hardening. However, with a few notable exceptions,5-7 direct observations of the Lomer lock and the L-C lock by electron transmission microscopy are scanty, and even these are subject to other interpretations.5,6 In a study of partial dislocations present in austenitic stainless steel, whelan8 did not observe any L-C locks at the head of pile-up groups. This result contradicted existing work hardening theories and led him to postulate an alternate theory based on the stress required to break away dislocations intersecting a pile-up group, from their stacking fault nodes. Due to the importance of the Lomer reaction in producing L-C locks which are an essential feature in current work hardening theories and because there exist no data giving direct quantitative values for the density of locks, and because there has even been some doubt expressed as to whether this important reaction occurs at all, a study of the dynamic behavior of the mixed dislocations which form the Lomer lock was undertaken. Due to their ability to cross-slip with relative ease, screw dislocations play an important role in the deformation of fee crystals. For this reason, the second type of reaction considered here is between screw dislocations of opposite sign. In addition, computations in volving screw dislocation interactions are relatively simple, thus providing a convenient check on the cornputational scheme employed. DEFINITION OF PROBLEM The force exerted on a dislocation due to a generalized stress field is given by the Peach and Koehler9 equation: Here t2 and b2 are respectively the tangent and Burgers vectors of the dislocation, and T1 is the stress dyadic defining the local stress field. The stress field may be externally applied or generated internally by the presence of a lattice defect, such as a second dislocation, as is the case in this work. Frank10 has shown that an equivalent momentum, P, of a screw dislocation can be defined by: Here, EST is the total energy of a screw dislocation and ESo is its rest energy. The left side of Eq. [2] is the time derivative of momentum and the right side is the position derivative of the energy due to the dynamical nature of the dislocation. The total energy of a dislocation is the sum of the potential and kinetic energies. Weertman11 has developed the expressions which were used here; these give the potential and kinetic energies of uniformly moving edge and screw dislocations in an isotropic medium.

Jan 1, 1969

By D. G. Oss, S. E. Erickson

An automatic control method for the ferrosilicon heavy media process maintains media density within 0.01 specific gravity points. Continued demands for higher grade, competitive products from the Mesabi Range have resulted in experimental work such as that detailed for one concentrator. Various methods, step by step procedures and instruments used at an iron ore beneficiation plant in the development of an automatic control system are described. Work continues and it is hoped that further applications of control instrumentation can be made in the next operating season. The need for instrumentation and automatic control of the various parameters in the heavy media process of iron ore beneficiation has been apparent for some time. Continued demands for higher grade, competitive products from the Mesabi Range have made it necessary to increase the efficiency of the process in every possible way. In a typical heavy media flow scheme for iron ore beneficiation (Fig. 1) a sized, prepared feed (generally about —1% in. to +% in.) is fed to a heavy media separatory vessel, along with a ferrosilicon slurry. A separation of the feed is made on the basis of specific gravity. Low density particles overflow a tailings discharge weir, while high density ore particles sink to the bottom of the high density pool and are moved away to the concentrate discharge chute. Both products are passed over drainage screens and then are cleaned thoroughly of attached ferrosilicon on wash screens. Float material is generally stockpiled, while the sink product is shipped as a final concentrate. Undersize from the drain screens is returned directly to the circulating media sump. Wash screen undersize is cleaned of contaminating ore particles and slimes by passing through magnetic separators. Provision is also made for splitting a portion of the tailings drain undersize into the cleaning circuit if necessary for control of depth of tailings overflow, or for additional cleaning as required. Cleaned ferrosilicon is stored in a densifier and returned to the Circulating media sump as make-up material. Dilution water is also added to this sump to maintain a desired specific gravity of the circulating media. As in any process, operational intelligence is secured only by keeping records of the process variables. Generally apeaking, plant operators have neither the inclination nor the time to keep complete and detailed records of these variables over the course of their shift. Before instrumentation was added to aid the operator, specific gravity was measured by weighing a given volume of pulp at intervals of from 30 to 60 min. Scale readings were made at the beginning and end of each shift. No records were kept of operating conditions, such as rpm of the separatory ves-sel, media level in the machine, tons per hour of the products, and so forth. These items were recorded only when spot checks were made by the metallurgical staff. CONTlNlJOUS DENSITY RECORDING The first process instrument used, other than the usual ammeter on the drive motor of the separatory vessel, was a nuclear density gauge and its associated circular chart recorder. These instruments were used to indicate and record specific gravity of the circulating media. This was a tremendous aid to the operator in that tie was able to observe and correct the specific gravity at any time. There was also added incentive to make frequent corrections because of the permanent record made by the recorder of the densities. The addition of the nuclear density gauge was influential in securing optimum quality and recovery of the heavy media product. Manual control was improved, and it became possible for a good operator to main control within f.05 specific gravity units. This compares with an unknown quantity, estimated at f0.15 gravity units, when manual measurement and control was used. An example of the improvement in manual control over the course of one season's operations is shown in Fig. 2. Chart A is typical of the records made shortly after the gauge was installed. Needless to say, it was difficult for operators and foremen alike

Jan 1, 1962

By J. W. Wolfe

The Benedict-Webb-Rmbin equation of state was used in digital computer programs to make rapid determinations of natural gas equilibrium phase compositions. Mixture components were the nine hydrocarbons, methane through heptane. Comparative tests were made with data from field separators, plant exchangers and literature sources. For most tests made, the B-W-R equations predrcted component K-vallles, mixture enthalpies and phase aensities within tile accuracy of available correlations for rune-component mixtures: significant deviations were noted when mixtures contained components heavier than heptune. INTRODUCTION Rapid, accurate methods for calculating the properties of hydrocarbon mixtures are needed for predicting the behavior of natural gas processes. For example, because of the common use of two-phase separation methods in gas proccssing, calculations must be made for the density and composition of equilibrium vapor and liquid phases. In addition, predictions must often be made for the temperature and pressure changes associated with the flow of single- and two-phase natural gas fluids through heat exchangers, chokes and turbines. The complex nature of non-ideal mixtures makes rigorous calculations for these natural gas properties difficult and time-consuming. Natural gas properties have conventionally been determined with generalized data correlations. These correlations, such as the K-values presented in the NGAA Equilibrium Ratio Data Book, are usually based on some average property of the mixture and have proven to give satisfactory estimates for the properties of most oil and gas systems. Digital computers, however, have not only increased the utility of these correlations, but also have made practical the use of equations of state for calculating the properties of natural gases. Potentially, if basic pure component data are available, all the desired thermodynamic properties of mixtures can be derived from a single equation of state describing the mixture. Currently. the best equation of state for describing the behavior of pure, light hydrocarbons over single-and two-phase regions, both below and above critical pressure, is that of Benedict. Webb and Rubin.' The equation contains eight constants which are determined by empirically fitting the equation to pure-component PVT data. Benedict and his co-workers presented the clevelopment of their equation as early as 1940.2 The B-W-R equation is a modification of the Beattie-Bridgeman equation of state and gives better PVT predictions than the Beattie equation at densities above the critical density. Benedict et al. made the equation applicable to mixtures by relating the mixture constants to composition and the constants for pure compounds. These authors, in a serics of articles in 1951,' showed the accuracy of the B-W-R equation when applied to light hydrocarbons and their simple mixtures, and demonstrated the equation's utility for making vapor-liquid equilibria calculations. Since its inception, the B-W-R equation has been the subject of many papers. Numerous additions and modifications have been proposed,'-',"'-':' the purpose of most being to improve the equation's ability to predict PVT properties of specific mixture systems. In 1959, Opfell, Pings and Sage summarized much of the work on the B-W-R equation in their book on equations of state." Since natural gases are primarily mixtures of light hydrocarbons, the B-W-R equation is a natural choice for an equation of state to compute both phase equilibria and thermodynamic properties of natural gases. Consequent-

Jan 1, 1967

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1946

By W. D. Robertson, H. H. Uhlig

The intermetallic compounds MgzSn and Mg2Pb are two of the important series of stoichiometric compounds which magnesium forms with elements of the fourth group of the periodic system. Since there is a complete series of compounds, all possessing the same comparatively simple structure, a unique opportunity is presented to study their properties with respect to increasing atomic number of the anion as it varies from silicon and germanium, through tin and lead. The present work deals with the two lower members of this group, and it is hoped eventually that additional data regarding the silicide and germanide will be obtained. The results of such a complete study provide part of the essential basis for the empirical correlation and theoretical treatment which, in other systems, has contributed to an understanding of inter-metallic compounds and the metallic'state in general. Some experimental data are already available in the literature. However, they are fragmentary and limited in significance owing to the methods of preparation employed and the impure materials available at the time. It was our objective, therefore, using pure metals and improved metallurgical methods of preparation, to produce stoichiometric compounds of high purity for the study of their electrical and chemical properties. We felt that a detailed investigation of chemical properties, about which relatively little is known, combined with electrical properties, would be a significant contribution to the understanding of these compounds and in particular to the mechanism of corrosion associated with types of bonding in alloy systems. The chemical studies are reported elsewhere. Previous Investigations Previous work concerning the electrical properties of these compounds was undertaken in connection with the establishment of the two phase diagrams which are available in Hansenl and Beck. The first comprehensive investigation of the electrical conductivity of magnesium-tin and magnesium-lead alloys was made by Kurnakov and Stepanov.3 This was followed by Grube and Voss-kiihler4 who studied electrical conductivity and thermal expansion over a wide range of temperature and who, unlike Stepanov, appreciated the significance of the large solid solubility of tin in magnesium and took some precautions to obtain an equilibrium state. However, at the time these investigations were made, neither pure magnesium nor

Jan 1, 1949

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1946

By Carl A Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By Albert R. Ledoux

In Great Britain all analytical chemists are styled assayers, but in the United states a slight distinction is made, assayers being considered those analytical chemists who have chiefly to do with the determination of the precious metals. There have grown up around the assayers of precious metals a number of customs and traditions which, as a rule, do not fetter American chemists when called upon to determine the composition or constituents of any samples submitted to them for analysis. In Great Britain, on the other hand, trade-customs even go to the extent of enforcing the employment of an admittedly erroneous atomic weight in certain alkali-determinations. If the American chemist is asked to determine the amount of lime in a water, potash in an alkali, or silica in an ore, the owner of the sample does not presume to suggest what method he shall employ, nor does he question his report on the ground that he should employ another method. But even in America it is different with the assayer. Unfortunately for the guild, as well as for those who have to base business operations on the reports of assayers, customs and traditions as well as divergent interests seek to circumscribe him in his choice of method and sometimes dictate how he shall perform his operations. This was true at one time of copper, which to-day in England is still determined by the so-called Cornish fire-assay, an attempt to imitate in the laboratory the various metallurgical operations in the smelting-works; but nowhere in this country is the assayer forced to employ any particular method for determining copper so long as his certificate indicates the true total percentage of copper in the sample. It is true that both buyers and sellers demand use of the electrolytic method, but only because it is the most accurate. In America the trade accepts the assayer's statement as final, and makes

Jan 1, 1895

By Pedro G. Salom

I HAVE had an opportonity, within the last few months, of making a large number of physical and chemical tests of steel for boiler and ship-plate, which has been, and is now being, used principally for the United States Government cruisers, now building in Mr. John Roach's yard, at Chester, Pa. Through the courtesy of the Messrs. Houston, of the Chester Rolling Mills, I have the honor to lay before the members of the Institate the results of these tests. These results have developed some points in regard to the nature of steel, which are more or less new, and which, I hope, will prove interesting. The original specifications, as regards the manner of testing, were so inipracticable (when their severity mas taken into consideration), that the keel of the first vessel, which will be launched next month, would, had they been carried out, probably not have been laid until next year. At my suggestion, in order to simplify and expedite the immense amount of testing that had to be done, the Naval Advisory Board was induced, after considerable discussion, to alter the specifications, so as to test each heat, instead of each lot of twenty plates, but reserved the right of making the quenching-test on a piece from each ingot, after it had been rolled. This relieved us from the anxiety of having a lot of plates rejected, after they had beell rolled and sheared, by reason of the presence of one or two plates which might have been injured in heating or rolling, or which might not have been able to stand the tests; while it insured the Government in obtaining a uniform quality of steel, and prevented the temptation to introduce a half-dozen or more had plates in a lot, and run the risk of their being selected as the testplates. I give below a portion of the original specifications, as prescribed

Jan 1, 1884

By Nichols J. Grant, Bill C. Geissen

In low temperature phase diagrams, liquidus curves below about 1500°C are relatively easily established, e.g., by thermal analysis or separation of coexisting solid and liquid phases, followed by chemical analysis. Experimental difficulties increase considerably at higher temperatures and in systems involving more reactive metals. Although there are now thermocouples available for use from 1600" to 2400°c, as summarized by Caldwell,' the need for frequent calibration, aging, and contamination problems, and unavailability of suitable protection tubes has sharply limited their use at higher temperatures. Many of the high melt- ing metals are found to react with refractory oxides. TO avoid such problems, a frequently used procedure is the diffusion and saturation method, as described by Spedding et a1.' for the system La-C. This technique involves the annealing of one metal or a suitable alloy in a crucible of the other element at a temperature above the melting point, followed by chemical analysis of the center of the melt, after equilibrium is established. Further, if an alloy system is to be investigated employing the electron microbeam probe, and calibration charts have been established, it may be possible to measure the alloy concentration at the center of a cored as-cast structure, and to conclude from this points on the liquidus curve in a manner similar to the one to be described. It is known that in phases with a broad homogeneity range the rapidly cooled, cored, as-cast structure of an alloy presents concentrations having different lattice constants; this spread of lattice constant values contributes to the broadened lines of a powder pattern for the as-cast condition. The region of the crystal which is first to solidify will then correspond to the edge of the lines if the change of the lattice parameters with concentration is monotonous. In the course of the determination of the Ta-Tr phase diagram,3 it became evident that such behavior made it possible to construct the

Jan 1, 1963

By Carl A. Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By P. H. Brace, N. A. Ziegler

The study of the relations between gases and metals is one of pcren-nial interest to all who are connected with the production of high-grade metallurgical products. The data reported here are the outcome of work of which the object is to determine the effects of dissolved gases upon the properties of metals and to gain a more detailed knowledge of the reactions between gases and molten metals, particularly iron, under definitely controlled conditions. We have attempted to reduce our margin of error by dealing with relatively large quantities of metal, from 4 to 13 Ih. (2 to 6 kg.), and keeping the ratio of refractories to metal as small as practicable. The ingots produced are large enough to provide adequate material for making determinations of magnetic and other physical properties. In choosing the bell-jar type of furnace we were influenced by the results of considerable experimentation along the same general line which indicated that, for the scale on which we were to work, it was important to have the furnace structure independent of the vacuum enclosure. The use of a bell-jar surrounding the entire furnace accomplishes this and also gives great freedom of observation during operation and ready accessibility for the replacements which are necessary after each run. Our choice of analytical method was made in the light of the results secured by H. M. Ryder, who used a method similar in principle for the analysis of very small quantities of gas extracted from strips of metal heated electrically in high vacuum. We have presented some selected preliminary experirnental data as being illustrative of the quantity and nature of the gases which occur in iron of different origins, but do not urgc any hypothesis at this time. The Furnace Our furnace may be described as "a high-frequency induction furnacc of the bell-jar type." It is similar in a general way to that described by Cain and Peterson1 though we have introduced certain refinements of

By L. G. Huntley

In view of the recent advance made in the knowledge of the nature and conditions accompanying the occurrence of oil and gas, and of the recent activity in drilling in Wyoming, Montana, and western Canada, a discussion of the probabilities of obtaining production in such a reservoir as the Dakota sand in general, and in particular districts, is thought by the author to be timely and likely to result in more intelligent operating in certain parts of the territory underlain by this sand. In Canada particularly it is thought that these general considerations have equal if not more significance in a consideration of the oil and gas possibilities of the formations than have the various local conditions. Age and Nature of Deposition of the Dakota Sand The Dakota is distinctive in that it is known to form a generally continuous sheet of sand underlying the greater part of Alberta, Saskatchewan, Manitoba, North and South Dakota, Montana, and large areas in Nebraska, Colorado, and Wyoming. It does not seem to have been laid down in more or less isolated lenses, as has been the case with most oil-sand horizons. Except in northern Alberta, the Dakota sand contains fresh-water fauna, having been deposited very uniformly over these wide areas in shallow water with prevailing strong currents. In northern Alberta marine and brackish water conditions prevailed. In this district it forms the basal member of the Cretaceous sediments, directly overlying beds of Devonian limestone along a great unconformity in the Athabasca River valley and eastward. In southern and western Alberta it is underlain unconformably by the Kootenay shales (Lower Cretaceous), and by Jurassic and Carboniferous rocks. In the United States in South Dakota it was in places deposited upon Cambrian quartzites, and in other places directly upon the granite. In the State of Dakota, and in the

Jan 1, 1916

By C. A. Siebert, D. J. Girardi

PRACTICALLY every metallurgical process in-volves, at some stage or another, the contact of a metal with a gas. Because of this, gas-metal re-actions are of great practical importance and have been subjected to numerous investigations. It has long been recognized that the presence of cuprous oxide in liquid copper has an important effect on its casting characteristics and .physical properties. This has led to the desirability of determining the quantitative relationships between cuprous oxide in the liquid copper and the usual gases present during processing. Such data are not only of practical importance but also of a theoretical interest in that they provide a means of applying the principles of physical chemistry to problems in applied metallurgy. The object of this investigation was to determine the quantitative relationship at equilibrium between the gases carbon monoxide and carbon dioxide and the cuprous oxide content of liquid copper. The reaction and its equilibrium constant may be expressed as follows: 2 Cu (liq) + CO2 (g) = Cu2O + CO (g) acu2o X aco/a2 cu X aco2 Here the underlined symbol Cu2O designates cuprous oxide dissolved in liquid copper and (a), the activity of the various constituents. The activities of carbon monoxide and carbon dioxide are assumed to be directly proportional to their re- spective partial pressures and the activities of cuprous oxide and copper are taken to be proportional to their respective mol fractions. The equilibrium constant may then be expressed as follows: K2 = Ncu2o X Pco [Ncu]2 X Pco2 where N = mol fraction The solubility of carbon monoxide and carbon dioxide in liquid copper is a rather controversial subject.'-' A review of the literature is given by 0. W. Ellis.' It appears that carbon monoxide and carbon dioxide are both only very slightly, if at all, soluble in liquid copper. Volskii and Slobodskoi5 determined the equilibrium between carbon monoxide, carbon dioxide, and liquid copper at 1100°C. Their results show a higher cuprous oxide content for a given CO/CO2 ratio than found in the present work. The system hydrogen, water vapor, and liquid copper was investigated by Allen and Hewitt8 over the temperature range of 1090" to 1350°C. Equilibrium values for the system carbon monoxide, carbon dioxide, and liquid copper calculated from these data agree reasonably well with the present work. Materials and Procedure The copper used was oxygen free, designated as OF and analyzed as 99.98 pct copper with no appreciable amount of any one impurity based upon spectrographic determinations. The carbon dioxide was cylinder gas averaging about 99.95 pct CO2 with air as the major impurity. The carbon monoxide was produced by passing carbon dioxide over heated charcoal. Alundum combustion boats were used as containers for the liquid copper. No appreciable reaction took place between the copper and the alumina. This was evident from the fact that the copper sample after a run did not ordinarily adhere to the bottom of the boat and that the

Jan 1, 1951

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By M. I. Jacobson, M. L. Hammond

The solid solubilities of high-purity silver, aluminum, chromium, copper, and iron in zone-refined beryllium have been determined. Diffusion couple sandwiches of beryllium with aluminum, copper, and silver foil and diffusion couples of beryllium with two-phase alloys in the Be-Cr. Be-Fe, and Be-Ag systems were analyzed by electron beam micro-probe techniques. This paper describes the material used, the experimental methods for preparing the diffusion couples and the alloys, the analytical techniques, and the results obtained. The results are compared with those of previous investigators who used materials of lower purity. ~NVESTIGATORS of beryllium phase diagrams have often been hampered in their interpretations of certain phase boundaries because of the relatively low purity of the beryllium used. This has sometimes resulted in the appearance of three phases in the regions where only two should exist. Advances in purification methods, specifically zone refining, have made available beryllium that is considerably purer than the material previously used for phase diagram studies. The primary object of this investigation was to reex-amine portions of the beryllium-rich end of the binary systems of beryllium with silver, aluminum, chromium, copper, and iron to determine more accurately the limits of terminal solid solubility. The five elements—silver, aluminum, chromium, copper, and iron—include some which are commonly found as the major impurities in beryllium, some of which are being used as solid-solution alloying elements, and some of which are used in ductile matrix alloys. They are thus of considerable importance to physical metallurgists who must work with beryllium but who must rely on the present inaccurate or incomplete diagrams. The determination of more reliable diagrams would aid researchers concerned with the problems of alloying, heat treatment, and ductility. MATERIAL The beryllium was acquired from the Franklin Institute in the form of a single-crystal, 6 in. long by 1 in. in diam, zone-refined in three passes from Pechiney SR-grade beryllium bar. The principal impurities, as determined by mass spectrography at Battelle Memorial Institute, are shown in Table I. Vacuum-melted copper, silver, and aluminum, and electron-beam zone-refined iron were obtained from the Materials Research Corp. in the form of 1/2-in.- diam bars. Iodide chromium was obtained as flakes from the Chromalloy Corp. Analyses supplied with these metals are shown in Table 11. EXPERIMENTAL PROCEDURE Preparation of Diffusion Couples. Two types of dif-fusion couples were used in this study. For the copper, silver, and aluminum systems, the couples were sand-

Jan 1, 1969

By G. E. Steudel

The study of the possibility of effecting a lower cost in the manufacture of pig iron reveals the importance of the ever present question of slag chemistry and volume. Factors that determine slag chemistry and volume are the impurities in the ore available, the ash-sulphur content of the coke, and a flux material necessary to promote removal of sulphur. Of these, the ores present by far the major source of impurities and what may prove to be the lowest practical slag volume with desired chemistry in one locality may be considered low or high in some other center of iron manufacture. The Chicago district is not only blessed with ores of high quality, but with excellent coke and flux materials as well. It is the intent of this paper to discuss slag problems at the South Works only, where burdens consist of Mesabi ores, Michigan stone, and coke ranging from 7 to 9 per cent ash and containing an average of 0.57 per cent sulphur. Early in the development of modern blast-furnace practice, the consideration of slags was secondary to the many adjustments of mechanical difficulties, such as furnace lines, stock distribution, stove design for obtaining higher blast temperatures, improved chemical segregation and size of raw materials. Furnace operators, after making these improvements, turned their attention to the study of other refinements in practice, of which slag chemistry appeared to be the most important. It is only within the last two decades that operators have become familiar with the various aspects of slag compositions. The industry, while rather slow in its recognition, is indebted to such investigators as Rankin,1 Wright,1 Feild,2 Royster,2 McCaffery,3 Kinney,4 Holbrook,5 and Joseph,5 whose researches concerning the elimination of sulphur within the blast furnace and the effect of slag composition upon melting point, viscosity, and desulphurizing power have established criteria for the selection of slags of the requisite quality. Large slag volumes result in higher coke consumption and cost of disposal. Any attempt to lower slag quantity must be accomplished

Jan 1, 1940