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By M. R. Geer, Franklin T. Davis, H. F. Yancey

COKE with low phosphorus content is required by some of the electrometallurgical and chemical plants recently attracted to the Pacific Northwest by the hydroelectric power available from Bonneville and Grand Coulee dams. Shipping such coke into the area from eastern points involves a high freight charge, and during wartime consumes precious rail and ship-bottom space, so it is highly desirable to produce coke from the coking coals of Washington to meet the requirements of these industries. Although coke has been made from Washington coals since 1884, little has been known about their phosphorus contents or about the extent to which phosphorus could be reduced by cleaning. An investigation was undertaken, therefore, to determine the manner in which phosphorus occurs in the coking coals of Washington and its amenability to removal by ordinary coal-washing methods. PREVIOUS WORK Phosphorus is a deleterious element in coke used for numerous metallurgical processes, including the production of pig iron, yet comparatively little published information is available on the occurrence and elimination of phosphorus in any of the coals of this country. A variation from 0.009 to 0.062 per cent phosphorus in various horizons of the Pittsburgh bed in the Connellsville region of Pennsylania has been reported,1 and a reduction in phosphorus content from 0.020 per cent in the raw coal to 0.018 per cent in the washed coal was obtained in washing coal from the same bed in the Pittsburgh area;2 the latter figures represent average analyses for a year's operation of the washery on about 800,000 tons of coal. A reduction in phosphorus content from 0.018 to 0.011 per cent in washing coal from the Pittsburgh bed at another washery was observed, and the same report provides data on the phosphorus reduction obtained by separating 10 other coals on a bath of 1.35 specific gravity.3 European investigators have been especially active in correlating phosphorus content with petrographic analysis; fusain and durain generally contain the highest percentage of phosphorus, but this relationship is not universal.4 Some of these investigators have found that phosphorus is removed in the coal-washing process,5 but others have observed that the clean coal contained as much or even more phosphorus than the raw coal.6

Jan 1, 1944

By Howard Scott

Manganese being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Arg transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the As transformation occurs at a tem-pcrature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3, quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Arg point as falling to 0" C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer," sing alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 per cent for the manganese content at which As is depressed to 0" C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By Laurence Hicks

CONSIDERATION of the past work on the subject of the diffusion of chromium into iron suggested that additional information might be given by the use of X-ray spectroscopy in following the concentration changes through the diffusion zone. Grübe and Fleischbein1 packed rods of electrolytic iron in a mixture of alumina and chromium. These specimens were heated in an atmos-phere of purified hydrogen for varying lengths of time. After treatment the specimens were examined metallographically and showed the usual structure, consisting of a border of radially oriented columnar grains ending in a sharp boundary line. Reference is made to the fact that etching with certain reagents will attack only the material inside the border of columnar growth and also to the fact that polishing seems to develop a ridge at the position of the boundary between the etched and unetched areas. By chemical analysis of thin layers turned off on a precision lathe, the authors were able to obtain depth-concentration curves. These curves, reproduced in Fig. 1, show that 'in most cases a pronounced change of slope occurs, corresponding to the position of the boundary of the columnar grains. In a later paper Grübe extends his work to other systems which show the same characteristics.2 He concludes that the reason for the break in the curve is that a hindrance of diffusion occurs at the place where the regularly oriented grains of the diffusion zone meet the random grains of the interior portion, on the assumption that the diffusion velocity in one direction in a grain may be greater than in another direction, and that the grains in the diffusion zone orient themselves so as to give the maximum diffusion rate. Kelley3 points out that Grübe has failed to note that the boundary line does not consistently cross all grains and

Jan 1, 1933

By Clarence Thom

This chapter presents, in summarized form, standard procedures for making separations of minerals from their ores by the froth flotation process to produce marketable concentrates. These are typical mineral separations which are being made commercially with the reagents and conditions generally used in the mining industry. Typical separations are presented for 17 metallic and 11 nonmetallic ores. The review of each includes a brief description of the mineral and the particular problem presented, general market specifications for its concentrates, an outline of treatment method, and kinds and quantities of reagents usually employed. This chapter does not include de- tails about ore preparation (crushing, grinding, and classification), elements of ore and pulp transportation (conveying and pumping), or concentrate preparation for market (thickening, filtering, and drying). In each presentation it is assumed, if not detailed further, that the ore is ground to the economical point of liberation of the minerals to be separated. Specific information, such as ratio of concentration and recovery, that depends upon the grade of ore being treated is considered beyond the scope of this chapter. Effective flotation separations that produce marketable concentrates may produce widely varying results in terms of percent recovery and still be economically profitable operations. Details of plant practice on specific ores are presented in Chapters 16 and 17. In this chapter the chemical names of the reagents are given. The extent to which different reagents are used in flotation plants in the U. S. is presented in Chapter 4. A compilation of the various flotation reagents, their trade names, manufacturers, and use has been prepared by H. T. Spedden. ANTIMONY The principal ore mineral of antimony, stibnite (Sb2 S3), is generally found in the U. S. in ore bodies in association with other valuable minerals such as galena (Pbs), sphalerite (ZnS), chalcopyrite (CuFeS2), or tetrahedrite (3Cu2 S – Sb2 S3), The sulfo-salt minerals of antimony, such as tetrahedrite or pyrargyrite, are often associated with high silver values, so that the presence of antimony may indicate economic importance even though the actual antimony content is low. Antimony is also significant to the mineral economy because of its occurrence in some ores where lead, gold, and silver are the

Jan 1, 1962

By H. H. Uhlig

Soon after general use of stainless steels began, it was observed in practice that certain combinations of factors tended to induce corrosion by pitting. For most applications this was a serious drawback, not so much because the structural properties of the metal were impaired but because of the rapidity with which heavy sections of the alloys were penetrated by small elongated pits. These pits seemed to initiate readily in oxidizing metal salt solutions like ferric chloride and in chloride solu-tions like sea water. It was observed that in sea water pitting was more frequent in stagnant or polluted waters than in highly aerated, moving waters. The steels in these chloride solutions were observed to be sensi-tive to long contact with material such as sand grains or attached bar-nacles. At points of attachment or contact it was not uncommon to discover initiation of corrosion. Pits once begun at contact faces were observed to grow rapidly, usually elongating phenomenally in the direc-tion of gravity until the metal was perforated. Hydrochloric acid and other nonoxidizing acids, on the other hand, were observed to corrode stainless steels generally; the weight losses often were higher, but the penetration less than for the pitting type of corrosion. The causes of pitting, a type of corrosion recognized as character-istic not only of stainless steels but of many additional metals and alloys, are important in corrosion studies. A possible explanation bears prac-tical significance, for once it is known why pits begin where they do and continue to grow after initiation, intelligent direction can be given to diminishing corrosion. This can be done either by some alteration in the composition and treatment of the alloy or by some alteration in the environment. It appears foremost in importance to discover the nature of pit foci, for if initiation of pits can be discouraged their growth will be no longer a factor to be considered. In a multi-component alloy containing many impurities normal to production of such an alloy, each of which may play a part in pitting, and whose corrosion resistance is sensitive to heat-

Jan 1, 1940

By Charles E. Parsons

One of the greatest factors in our industrial development is cheap and convenient power. Long-distance electrical transmission has now reached such a stage that it is feasible, and practicable, to utilize the water-power of the country which was heretofore too remote for consideration. In all of the changes of energy from its various sources to its electrical applications, water-power stands pre-eminent in point of economy. Power-users the world over have endeavored to utilize this force in preference to any other, and until long-distance transmission was found practicable it seemed that every available water-power in this section of the country was doing its full share for the benefit of mankind. The success of each great industrial development has been clue in a greater part to some one man one who is just a step in advance of the rest in his particular field; one who is able to grasp a situation and foresee possibilities; and, above all, one who has that indomitable pluck and perseverance which sees in each obstacle one more step toward success. Such a mail is Eugene L. Ashley, for it was through his efforts that the development of the greatest power on the Hudson river was made possible. For several years prior to 1897 the various properties along the river between Glens Falls and Palmer Falls were in the hands of speculators. These men knew the value of waterrights, but they had not the ability to assemble the properties and finance such an undertaking. In 1897 Mr. Ashley began buying these water-rights, and, after two years of litigation, title mas secured to all of the properties along each side of the river, and the Hudson River Water-Power Company was organized to construct a dam and transmit power to the surrounding cities and villages. A contract was let for a dam

Jan 1, 1904

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By J. W. Spretnak

It is well-established that decohesions occurring at the interface of the matrix and rigid inclusions and second-phase particles are prime causes of ductile fracture initiation. It is not clear, however, how these decohesions occur. The idea that the interface bond is broken in tension is not particularly attractive when one considers the strength of such interfaces and the fact that plastic flow is not restricted under conditions of continuing flow required to initiate and propagate ductile fracture. A suggestion as to the mechanism of decohesion arises if one takes the position that, as the dislocation density increases with plastic flow and reaches some critical range of density, the phenomenon of flow can be regarded as fluidlike instead of the crystallographic motion of dislocations. As the spacing between dislocations decreases, the matrix becomes increasingly disordered in terms of loss of periodicity. At some critical degree of reduction of the periodicity, it is suggested that flow can be regarded as hydrodynamic, rather than crystallographic. Such a state has been referred to by rheologists as the "plasticized state", or the "fourth state of matter", between the liquid and solid state. A similar argument pertains qualitatively with the increase in equilibrium vacancy concentration as the temperature approaches the melting point. Taking the viewpoint that at larger strains the flow may become hydrodynamic in nature, a mechanism of decohesion is suggested. A well-known phenomenon in boundary-layer flow is that of "separation" locally of the boundary layer from the substrate.' Under certain conditions, the flow in the immediate neighborhood of the substrate becomes reversed, causing the boundary layer to separate from it. The exact condition for separation is that the velocity gradient normal to the substrate vanishes there, or It is of interest that blunt particles such as spheres and circular cylinders are most likely to give rise to separations because of unfavorable pressure distributions behind them. The source cited gives solutions for positions of separations for various geometries. In principle, such separations can also take place when metal is flowing over a "dead zone" of stagnant metal. This may explain the initiation of fracture at the elastic-plastic boundaries of plastic enclaves under a notch.

Jan 1, 1967

By H. M. Rutherford

THE reflection method in seismic prospecting has aroused much interest in the past few years. The purpose of the present paper is .to present the method of reflections in the mapping of geologic structure and also to give some indication of its limitations. The reflection method is well adapted to the mapping of geologic structure in the Mid-Continent fields, and has been found most useful there. The refraction method is ideally suited to the finding of structures, such as domes, where the amount of relief is very large. This explains the brilliant success of the refraction method in the Gulf Coastal region of Texas and Louisiana. The additional fact that salt has a much higher velocity than the sur-rounding sediments made their discovery much easier. By the use of the reflection method, differences of relief of 25 to 50 ft. to the mile may be detected at a depth of 5000 ft., and the depth points accurately plotted on a map. This is hardly possible by the use of the refraction method. The reflection method has been in almost continuous use in the Mid-Continent area since 1926, but very little, if anything, has been published until recently(7) ? regarding either the method or the results. The dis-covery of several oil fields is now attributed to the use of the reflec-tion method. Reflection methods have been used by the Germans to find the thick-ness of the ice of several glaciers. (2,8) The depths there considered were of the order of only a few hundred feet. For the method to be of any practical value in this country, it must be able to work to depths of several thousand feet. As was indicated above, this is now possible, though there are many problems connected with the reflection method yet to be solved. The refraction method requires that the shooting be done over long ranges. It was necessary, for example, to take distances out to several miles in order to penetrate some five thousand feet. Naturally this uses a good deal of dynamite. In the reflection method the distances are much shorter and the amounts of dynamite are much smaller, within limits which will be noted below. The chief distinction between refrac-tion and reflection methods is to be found in the analysis of the seismo-gram. Refraction shooting makes use of only the first arrival of energy

Jan 1, 1932

By George G. Binder Jr., James W. Lacey, Arthur L. Draper

An experimental investigation of miscible fluid displacement has been made in linear porous media under highly adverse mobility ratio conditions. Various refined oils were displaced at field rates by liquid propane in both horizontal and vertical models 9 to 36 ft in length. In horizontal tests, mixed zones or transition zones form between the two liquids early in the displace-lents. Initially, the zones grow rapidly. III 2-in. diameter models, the mixed regions become nearly stable zones from 6- to 20-ft long. From then on these quasi-stable zones apparently grow only by molecular diffusion. The lenghts of the quasi-stable zones appear to be almost independent of the core material in which displacement;; are made and increase with increasing rates of injection and oil/solvent viscosity ratios. The lengths of the quasi-stable zones. measured in 2-in. diameter models at viscosity ratios and injection rates anticipated in the field indicate that essentially piston-like displacements of oil by solvent would occur. However, the mixed zone lengths increase markedly as the model diameter increases. In vertical displacements controlled by gravity drainage, only short trans-sition zones form. The entire lenghts of these zones can be accounted for by molecular diffusion. Therefore, in reservoirs having characteristics allowing a high degree of gravity drainage, nearly complete oil recovery should be attainable by miscible fluid displacement. INTRODUCTION The oil industry is faced with an ever increasing cost for finding new oil reservoirs. This, coupled with the fact that conventional methods of oil recovery usually leave from 1 to 3 bbl of oil in the ground for every barrel produced, has aroused considerable interest in developing more efficient methods. An integral part of the mechanism of many of these new methods of recovery is a miscible fluid displacement in which oil is displaced by a much less viscous materiai such as liquid propane. A numher of irlvestigators have explored the mechanics of miscible fluid displace-ment,'.2.1.'."." but in the experiments reported many of the important factors have been varied only over a limited range far removed from norma1 oilfield values. This paper presents the results of an experimental study of oil displacement by liquid propane at field rates from linear, natural-sandstone models of various sizes. Both horizontal and vertical flow tests were made. EXPERIMENTAL APPARATUS AND PROCEDURE Refined oils with viscosities varying over a wide range were displaced at several rates by liquid Propane from both horizontal and vertical flow systems. The behavior of the displacement was observed by propane-oil analyses of the effluent and, when possible, by differential pressure measurements along the cores. A schematic flow diagram of the apParatus used to conduct the experirents is shown in Fig. 1. The cores used in the tests were 9-ft lengths cut from natural consolidated sandstone and turned to the desired diameter. These were cast in steel tubing with a low melting point (160°F) alloy which expands on solidification. Flanges welded to the ends of the steel pipes permitted sealing the ends or butting one core to another. Pressure seals were maintained with O-rings. The cores were cleaned by flushing

By George Stanley Scott

Many requests for information as to the possibility of washing coals to some predetermined percentage of ash or sulfur have suggested that the producers aim to satisfy some degree of purity set by the user of the fuel, rather than to attain the greatest economic benefit to all concerned. This paper is written to show that the highest economic purity of washed coal can be determined from washability studies of the raw coal, costs of mining and washing coal, and data on the effect of ash and sulfur on the value of the coal for the particular use for which it is intended. Coke fob Blast-fuenace Use For purposes of illustration, we take the case of coal washed for coke to be used in the iron blast furnace. The method outlined can be made general in its application by substituting for the figures used here the actual operating figures for the particular case under consideration. In general, it costs the blast-furnace operation from 8 to 25 c. per ton of pig iron to slag out each 1 per cent. of ash introduced into the blast furnace by the coke. This figure depends on which one per cent. of ash is removed, and decreases with decrease in ash. When blast furnaces and coal mines are considered as a whole, the figure decreases to zero and then becomes negative, on account of low recovery of washed coal. Various figures1 have been given by different investigators. These figures necessarily differ, not only on account of the differences in operating costs but on account of the difference in the respective fuels as well. For the purpose of this paper, which, as explained, is to point out a method of attacking a certain problem, the figures used in the exposition of the method are of secondary importance. It is apparent that no universally applicable figures can be used, because there are none. Each plant has its own coal,2 its own operating cost, and its own conditions.

Jan 1, 1930

By David Cornell, Yusuf K. Sukkar

The fundamental differential equation for fluid flow has been rearranged, integrated numerically for natural gases, and the results presented in tabular and graphical form suitable for the direct calculation of vertical gas flow problems. The integration is rigorous except for the use of a constant average temperature. Both static and flowing bottom-hole pressures may be calculated by (his method without resort to trial and error procedures. INTRODUCTION Bottom-hole pressures can be determined either by direct measurement with a bottom-hole pressure gauge or by calculation. Since measurement with a bottom-hole pressure gauge is costly, calculation of bottom-hole pressures is to be preferred when possible. Calculation involves knowledge of the wellhead pressure, the properties of the gas, the depth of the well, the flow rate, the temperature of the gas, and the size of the flow line. These quantities must be combined in a suitable equation for vertical flow. Several equations have been developed for the purpose of calculating gas flow through both horizontal and vertical pipes1,2,4,5,6,7,8,9 These equations all have the basic differential equation for flow as their starting point. They differ only in the assumptions which are made in order to simplify the integration step. The bottom-hole pressures calculated using any of the better known equations are in good agreement with bottom-hole pressures calculated by a more rigorous but considerably more tedious stepwise integration method. All of these methods, however. require a trial and error solution for the calculation of flowing bottom-hole pressures. The purpose of this paper is to present a method which provides a direct solution of static and flowing bottom-hole pressures without use of a trial and error solution. At the same time the method involves fewer simplifying assumptions than any of the previous methods used, except lor the lengthy stepwise method. The derivation of any practical flow equation begins with the basic differential equation which is rigorous for almost all flow problems. The five terms in Equation 1 represent the potential energy, the potential energy of position, the kinetic energy, the shaft work done, and the energy losses due to motion of the fluid respectively. Equation 1 reduces to Bernoulli's theorem for the case of horizontal flow of an incompressible fluid, no work done, and no energy losses due to friction. In the present case, the term (v) (dv)/(g,.) can be shown to be quite negligible compared to the other terms, and is therefore neglected in the derivation. The term — dws includes work done by a pump or turbine in the system and is zero in this case. The frictional losses in the pipe are included in the term — d(lw) which is expressed in terms of the Moody friction factor as in Equation 2. (f) (v2) (dL) d(lW) = (f)(V2) (dl)/(2) (g) (d) The specific volume of a gas can be expressed in terms of the temperature, pressure, molecular weight, and compressibility factor. The velocity of the gas can be expressed in terms of the weight rate of flow, the specific volume, and the dimensions of the pipe.The reduced pressure Pr is to be used because z can be expressed as a function of Pr and Tr alone for most natural gases:

Jan 1, 1956

By Maxwell Gensamer, Vsevolod N. Krivobok

It is generally recognized that "low temperatures" have a definite effect on the properties of metals and alloys. Furthermore, it is also generally understood that the effect is decidedly adverse. The possibility that the same low-temperature treatment might be employed for the purpose of improving certain properties of the alloys has received less attention until recently, and the experimental and theoretical knowledge consequently is meager. The effect of low temperatures may be studied in two ways: by studying such properties as tensile strength, hardpess, impact resistance, etc., at low temperature, and by studying the properties of alloys at room temperature after these alloys have been subjected to a low-temperature treatment. Even in the latter case, certain properties will differ materially from the same properties obtained on identical material but without cold treatment. In other words, subjecting alloys to cold treatment results in an irreversible change in mechanical properties. Changes of this character are usually indications of the appearance of a new phase or phases, and would be likely to occur in alloys which, either by virtue of their composition or by heat treatment, are retained at room temperature in a metastable condition. Consequently, studies of the effect of low temperatures logically should be conducted from the physicochemical point of view, since the results of such studies not only would furnish metallurgists with interesting theoretical data but would clearly indicate the classes of alloys that would hold promise of improvement, and, possibly, of new applications. As the present investmigation deals with chromium and chromium-nickel alloys of iron of the stainless variety, it has been thought desirable to present the data concerning low-temperature properties of these alloys, available from the most recent and most comprehensive work of H. S. Russell.l A summary of these data is given in Table 1. The data are confined to a limited number of alloys of the type dealt with in the present

Jan 1, 1931

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 W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By Richard H. Siller, Rex B. McLellan

A model for interstitial solid solutions has been considered in which a repulsive Potential exists between interstitial atoms in the solvent lattice. It has been shown that this model is consistent with the thermodynamic Properties of certain interstitial solid solutions. The model is then applied to the calculation of the variation of the diffusivity of carbon in au-tenite with composition. Although the energy levels at the saddle point, and thus the absolute values of dif-fusivity, cannot be calculated, it is shown that by taking the repulsive interactions between the diffusing atoms into account the functional form of the dependence of diffusivity on solute concentration can be derived. ThE composition dependence of the diffusivity, D, of carbon in austenite at a given temperature is well-known.'-3 smith3 tried to reconcile the observed composition dependence of D at 1000°C with the previously observed4 composition dependence of carbon activity using equations for D derived by arken5 and Fisher, Hollomon, and Turnbull,6 but was unsuccessful. In this paper we shall modify the approach of Fisher et al. by considering the "blocking" model7 for interstitial solid solutions, based on concept due to Speiser and Spretnak,' in which a repulsive potential exists between interstitial solute atoms in the solvent lattice, causing a certain number of interstitial sites to be "blocked" from occupancy by further solute atoms. We shall thus be able to describe the intimate relationship between the composition dependence of carbon diffusivity, a kinetic phenomenon, and the composition dependence of carbon activity in austenite. THEORY Consider for convenience one-dimensional interstitial diffusion in an fcc lattice in the [loo] direction. Fig. 1. Assume that solute atoms occupy octahedral sites only.7,9'10 These octahedral sites are located on {lOO} planes a/2Å apart. A solute atom, A, occupying an octahedral site on a {100 } plane denoted by 2, has twelve nearest-neighbor octahedral sites: four on plane 1, four on plane 2, and four on plane 3. Diffusion occurs when there is a net flux of solute atoms, through an imaginary plane shown with dashed lines, from plane 2 to plane 3. Fisher et al6. use the concept of activated complexes, as given in the theory of absolute reaction rates." They show that the number of solute atoms per cubic centimeter per second which pc — Fig. 1-Diagram showing the arrangement of octahedral sites (x) in the fcc lattice. pass in the direction of diffusion from activated to new interstitial position is: ?where C is the concentration of the solute in atoms per cubic centimeter, l/m + is the fraction of new interstitial positions corresponding to motion in the forward diffusion direction (transmission coefficient), ?F* is the free-energy difference between the activated complex and the reactants when each is in its standard state at the temperature of the reaction (independent of temperature and composition in the case of carbon in austenite), y is the activity coefficient of the solute species, and, finally, ym is the activity coefficient of the activated complex (assumed constant). The flux of atoms moving in the forward direction through an area of 1 sq cm perpendicular to the direction of diffusion is therefore: m+ Ym l ' atoms per second where is the distance between planes. The blocking model states that a nearest-neighbor octahedral site of a given solute atom has a probability, f, of being inaccessible to other solute atoms. The number of available sites for diffusion on a given plane will, therefore, depend on f, which is constant, and Nu, the number of solute atoms on that plane. The effect is to have more available sites in the diffusion direction, thereby increasing the net flux of solute atoms. This is reflected in the transmission coefficient, l/m. To calculate the transmission coefficient for solute

Jan 1, 1970

By D. C. Jillson

WORK in recent years1-' has indicated a complexity of the processes of deformation of metal crystals not previously appreciated and not fully accounted for by any hypothesis so far advanced. Furthermore, the nature and mechanism of formation of nuclei of recrystallization have not been determined precisely. The deformation of single crystals of zinc has been studied frequently, but the purity of the zinc and the perfection of the specimens sometimes have been given little consideration. Methods have been developed recently that readily yield zinc single-crystal specimens of high quality.5 In the present work, such specimens were deformed in various ways under various conditions, and deformed specimens were annealed to obtain information regarding recovery, recrystallization, and grain growth. The paper attempts to correlate and evaluate previous data, as well as to present new data, in order to determine areas in which more detailed work might be done most profitably. Tests at temperatures from the freezing point (419.46°C) to room temperature revealed glide only on basal planes in a close-packed direction (100)*, as reported by Mark, Polanyi, and Schmid6 and others. Markings probably similar to those observed by Kolesnikov7 and Boas and Schmid8 were noted in specimens stretched at elevated temperatures, but it seemed clear that these were not caused by prismatic or pyramidal slip (see second paragraph of section on Phenomena Involving Bending of the Basal Plane). Twinning Twinning on the octahedral plane of a face-centered cubic metal has been pictured as a process of simple homogeneous shearing along that plane in a [112] direction. It was recognized by Mathewson and Phillipsv and others""" that the (102) twinning of zinc required a somewhat more complex mechanism and might be considered as a homogeneous shearing of (102) planes in a [211] direction plus slight adjustments of atoms to positions of greater stability or lower energy, or as a single movement of each of the atoms in the same sense into the final positions. Gough and Cox" modified Mathewson's mechanism to obtain a more stable lattice configuration, but it is not clear that they succeeded, and their mechanism requires movement of some of the atoms in a sense opposite to that of the overall twinning movement. They also suggested that twinning may occur as a result of previous basal slip. This conclusion was based on the observation that twinning caused by alternating torsion was clearest and most profuse at positions for maximum basal slip rather than for maximum stress on (102) planes in the close-packed direction (not the twinning direction), and no mechanism was described. It might be wondered whether resolution of stresses on the twinning plane in the twinning direction would have afforded a simpler explanation. If twinning is essentially a simple homogeneous shearing along the twinning plane, it would seem that twins should grow by a smooth, continuous mechanism, and, indeed, that a simple reversal of stresses should reverse the shearing and de-twin the crystal. Cylindrical tablets 1/8 to 1/4 in. thick were cleaved from singlle-crystal specimens and were squeezed, perpendicular to a second-order prism plane, to give a tensile stress perpendicular to a first-order prism plane. A "click" was heard and a thin, needle-like twin appeared on the basal cleavage face. If squeezing was continued smoothly, the twin, viewed at magnifications up to X500, grew smoothly and quietly (fig. 1). X-ray examination verified that the twinning was of the (102) type. Rotating the compression axis 90" to reverse the stress then caused a smooth, continuous shrinkage and ultimate disappearance of the twin (fig. 2). The squeezing also caused a rumpling of the basal

Jan 1, 1951

By Henry M. Howe

This paper is a discussion of the extremely valuable one of Mathewson and Phillips, The Recrystallization of Cold-Worked Alpha Brass on Annealing,1 which not only gives us a wealth of important data reached with great intelligence, but also shows both uncommon powers of imagination and a perfectly fair spirit. Let me try to analyze some of their results, and to enunciate some of the laws to which these results point. For brevity I refer to them as "The Authors." The page numbers in parentheses refer to their paper. 1. The Visible Aspects of Recrystallization.—Plastic deformation in a single direction, as in cold-rolling, draws the grains out in that direction, that is, inequiaxes them, without destroying their apparent individuality. Each grain seems to endure the drawing out without changing either its volume or its orientation materially, for the etching tint of each grain seems to be as uniform after as before the drawing out, save for the "etch bands,"2 shown in Figs. A to D of the Authors' Plate I. As the drawn-out metal is heated progressively, on reaching a certain "disintegration temperature" these old grains seem to break up, probably into submicroscopic fragments, and this apparent disintegration is followed by a coalescence of these fragments, so that their number decreases and their size increases, till they may become very much coarser than before the drawing out. Ruder3 coarsened the grains of silicon steel in this way till single grains reached an area of 50 cm. (7.75 sq. in.). The deformation itself probably breaks each grain up into many very small fragments, but the fact that each grain continues to have a uniform etching tint different from that of its neighbors indicates that these fragments retain the initial common orientation of the grain. The apparent disintegration which we observe, then, is rather an abandonment of community of orientation for individuality of orientation, by the fragments formed earlier during the deformation. Hence we

Jan 1, 1917

By Oliver Bowles

When a new type of equipment revolutionizes methods of quarrying one kind of stone, producers of other kinds focus their attention on its potentialities in their particular fields. The purpose of this paper is to discuss the accomplishments of the wire saw in slate, to show its more limited attainments in other kinds of stone, and to point out the possibilities of much wider application. A wire saw consists of a 3/16-in. or ji-in. three-strand wire cable that runs as a belt and cuts the rock by abrasion. (Fig. 1. The teeth of the saw are sand grains carried in the grooves between the strands. Accomplishments in Slate† Initial experiments with wire saws by the U. S. Bureau of Mines in the Colonial Slate Quarry, Wind Gap, Pa., in 1926, attained success so immediate and pronounced that within two years in virtually every quarry in the neighborhood of Wind Gap, Pen Argyl and Bangor, the most productive slate area in the United States, wire saws were substituted for channeling machines. An 80-ft. cut in slate is shown in Fig. 2. The technique of operation has been described in several reports (references at the end of the paper). The present purpose is to summarize the accomplishments in a large, typical slate quarry after nine. years of experience. Parsons Bros. Slate Co., at Pen Argyl, Pa., substituted two wire saws for six channeling machines in 1927. The following comparisons are made between the present method with wire saws and the former channel-ing-machine method. Rate of Sawing.—The average rate of cutting with a wire saw in the early days of its operation, as determined by the Bureau of Mines', wits 14 to 17 sq. ft. per hour. Parsons Bros. Slate Co. estimates the present rate of cutting at about 25 sq. ft. an hour, whereas the channeling-rnarhirle

Jan 1, 1938

By Oliver Bowles

When a new type of equipment revolutionizes methods of quarrying one kind of stone, producers of other kinds focus their attention on its potentialities in their particular fields. The purpose of this paper is to discuss the accomplishments of the wire saw in slate, to show its more limited attainments in other kinds of stone, and to point out the possibilities of much wider application. A wire saw consists of a 3/16-in. or ji-in. three-strand wire cable that runs as a belt and cuts the rock by abrasion. (Fig. 1. The teeth of the saw are sand grains carried in the grooves between the strands. Accomplishments in Slate† Initial experiments with wire saws by the U. S. Bureau of Mines in the Colonial Slate Quarry, Wind Gap, Pa., in 1926, attained success so immediate and pronounced that within two years in virtually every quarry in the neighborhood of Wind Gap, Pen Argyl and Bangor, the most productive slate area in the United States, wire saws were substituted for channeling machines. An 80-ft. cut in slate is shown in Fig. 2. The technique of operation has been described in several reports (references at the end of the paper). The present purpose is to summarize the accomplishments in a large, typical slate quarry after nine. years of experience. Parsons Bros. Slate Co., at Pen Argyl, Pa., substituted two wire saws for six channeling machines in 1927. The following comparisons are made between the present method with wire saws and the former channel-ing-machine method. Rate of Sawing.—The average rate of cutting with a wire saw in the early days of its operation, as determined by the Bureau of Mines', wits 14 to 17 sq. ft. per hour. Parsons Bros. Slate Co. estimates the present rate of cutting at about 25 sq. ft. an hour, whereas the channeling-rnarhirle

Jan 1, 1938