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By J. G. Benford, E. B. Stanley

THERE have been numerous papers in the literature1 on the subjects of secondary and tertiary recrystalli-zation in silicon steels. Secondary re crystallization is believed to occur in silicon steel by either a surface-energy phenomenon such as in the usual development of cube texture or by a second-phase phenomenon such as in the usual production of cube-on-edge texture, (110)[001]. Tertiary recrystallization in silicon steel is thought to be a surface-energy phenomenon in which, for example, grains having a (110) plane parallel to the sheet grow at the expense of other grains in the matrix including those having a (100) plane parallel to the plane of the sheet. In all these instances, the orientations involve either a preferred (100) or (110) plane in the plane of the sheet. Until very recently, there had been no experimental evidence reported of the occurrence of a texture by secondary or tertiary recrystallization that involves a (111) plane in the plane of the sheet, although Kohler reported that grains having the (111) plane parallel to the sheet surface can also grow by a surface energy mechanism. Stickels observed a secondary texture in iron described as "near {554}(225)" about 5 deg from {lll}(211).3 Mee reported that in a vacuum-remelted commercial 3 pct Si steel {lll}(hkl) secondary recrystallization took place in a high vacuum and in pure hydrogen.4 Recently in our Laboratory, large-grained structures such as shown in Fig. 1 having an orientation near (111)[211] or (111)[2ii] have been observed. The arrows point to areas of relatively small matrix grains of the kind that the much larger (111) grains consumed while growing. It is of interest that the matrix grains of samples annealed at 2000°F were essentially the same size as those in samples annealed at 2200°F, a matrix-grain-size stability that is characteristic of secondary recrystallization processes. A torque disc taken from Grain 4 of the sample shown in Fig. 1 revealed a very flat magnetic-torque curve, as expected, with a maximum torque of 7000 dyne-cm per cu cm compared to the typical 180,000 dyne-cm per cu cm observed for conventional (110)[001] textured material. A back-reflection Laue pattern for Grain 4 is shown in Fig. 2 and indicates a near-perfect (111)[211] orientation. The other six numbered grains in the sample of Fig. 1 had a similar orientation. The small circles next to each number were the target areas for the X-ray beam. The starting material was an 0.011-in.-thick oriented silicon steel, (110)[001] texture, containing 3 pct Si. It was lightly pickled, cold-rolled to 0.005 in., and annealed 4 hr at 2200°F within a nickel box (not gas-tight) inside a tube furnace through which dry hydrogen was flowing. The samples were heated to 1500°F in 1 hr and then at 60°F per hr to 2200°F. There were other

Jan 1, 1969

By H. C. Chao, Y. E. Smith, L. H. Van Vlack

ThE phase relationships for the MnO-MnS system have been investigated only in the eutectic region. wentrupl reported a eutectic at 1280°C (2345°F) with approximately 50 wt pct of each component, as based on the earlier work of Andrew, Maddocks, and Fowler.2 More recently silverman3 corrected these figures to 2275° ±10°F (1246°C) with 63 wt pct MnS and 37 pct MnO. Neither Wentrup nor Silverman investigated the solid-solution limits in this system. However, Wentrup did suggest with his phase diagram sketch that the maximum solubility of MnS in MnO is 10 wt pct, and the solubility of MnO in MnS is nearer 20 wt pct, Fig. 1. These figures have been utilized in subsequent publications without further verification.4 There had been evidence found in this laboratory that the above solid-solution figures were high. An investigation was therefore conducted using the following procedure. Samples containing MnO and MnS were contained in platinum foil, heated just above the eutectic temperature in a purified nitrogen at- mosphere, and quenched into distilled water. The MnO had been prepared by calcining reagent grade MnCO3 in nitrogen at 1400°C. Only MnO was detected in subsequent X-ray diffraction analyses. The MnS had been prepared by sulfur deoxidation of reagent grade MnSO4 according to the reaction: MnSO4 + S2 ? MnS + 2SO2 The details of the sulfide preparation procedure, which utilized atmospheric sulfur pressures at 950°C, are discussed elsewhere.5 The sulfur content of the sulfide was determined to be 36.8 * 0.2 pct, which matches the stoichiometric value of 36.9 pct. No evidence of either MnO or MnSO4 was detected microscopically or by X-ray diffraction. The single-phase combinations of MnO and MnS at the eutectic temperature indicate the limit of solid solution as shown in Fig. 2(a) and (c), and the revised phase diagram is shown in Fig. 2(d). The melting temperature for MnO is that provided by Glasser.6 The eutectic temperature of 1232° ± 5°C and eutectic composition of 64 wt pct MnS are in close agreement with Silverman's correction of Wentrup's work. The maximum solubility of MnO in MnS was determined to be 1.7 ± 0.2 wt pct. The maximum solubility of MnS in MnO was determined to be 1.8 ± 0.2 wt pct. These figures represent the lower limit for the presence of liquid at 1260°C and are significantly lower than the earlier estimated solid-solution figures. The authors wish to acknowledge the support of U.S. Steel's Edgar C. Bain Laboratory for Fundamental Research. The comments and critical suggestions of Drs. A. S. Keh, R. Rickett, and R. B. Snow are appreciated.

Jan 1, 1963

By D. Hnrrington

THE Dust Symposium was attended by approximately 100 persons, nearly all of whom remained from the starting hour (2 p. m.) until the use of the auditorium was demanded for another meeting at 5:30 p. in. In calling the meeting to order, D. Harrington made a few remarks as to the importance of the health dust problem in mining as well as in general industry and expressed gratification that the subject is now out in the open and that mining people are desirous of ascertaining the facts. B. F. Tillson acted as chairman of the meeting. The milling executive who desires to know what to do to prevent his workers from being unduly exposed to the dust hazard can get much out of the paper by D. E. Cummings, who has been doing much work in mines trying to keep -the dust in the air within safe limits. His recommendations indicate that the main protection of the worker in mines is by adequate ventilation, supplemented by the extensive use of water in drilling, as well as in water curtaining to condition air both in regard to dust content and to temperatures. Blasting was shown to be one of the chief causes for dust and it was recommended that whenever feasible all blasting should be delayed to the end of the working shift.

Jan 1, 1935

By George V. Smith, Daniel E. Sonon

Various mechanical properties of the Ni-Co-C alloy system were investigated to delineate the strengthening effect of carbon. Carbon concentration, cobalt concentration, vain size, temperature, and strain rate were varied so that thermal activation analysis and the Hall-Petch analysis could be used to evaluate the strengthening effect of carbon. Increasing carbon increased the strength of nickel and a Ni-60 pct Co alloy , with the effect becoming more pronounced at lower temperatures. Yield stress depended linearly on carbon concentration in nickel, but it depended on the square root of carbon concentration in the Ni-60 pct Co alloy. The Hall-Petch slope of nickel increased with carbon concentration; however, that of the Ni-60 pct Co alloy did not. The yielding behavior of these alloys was sensitive to composition, grain size, and temperature. Cobalt eliminated serrations in the flow curve of carbon-containing nickel at 300' and weakened them severely at higher temperatures. Pairs, or clusters, of carbon atoms appear to be responsible for the observed strengthening behavior. FLINN' conducted several experiments with carbon in nickel in an effort to provide information on the strengthening effect of interstitial impurities in solid solution in fcc metals and alloys. Strengthening which increased with decreasing temperature led him to conclude that carbon causes Cottrell locking in nickel. Fleischer2 analyzed Flinn's data and calculated that the strengthening effect of carbon in nickel was smaller by a factor of fifty than the strengthening effect of carbon in a! iron. Fleischer2 termed the magnitude of strengthening of carbon in nickel "gradual" and that of carbon in a! iron "rapid". He attributed "gradual" hardening to hydrostatic strains and localized changes in modulus of elasticity around solute atoms, whereas he attributed "rapid" hardening to tetragonal strains around solute atoms. Sukhovarov et a1.3-7 reported strain aging and serrated plastic flow in nickel, both of which they attributed to the presence of carbon. Serrated plastic flow has been rationalized by a process involving a series of dislocation pinning and multiplication steps.8, This process is more probable when screw dislocations are strongly pinned. Screw dislocations cannot be pinned by pure hydrostatic forces from the symmetrical strains of an interstitial impurity in an fcc lattice, except for small, second-order effects. However, they might be pinned by localized changes in modulus of elasticity around solute atoms,' by the pinning of the edge components of the partial dislocations of an extended screw dislo~ation,'~ or by clustered groups of solute atoms whose net elastic stress field is unsymmetric. The purpose of the present work was to investigate various mechanical properties of the Ni-Co-C a1loy system which are sensitive to pinning effects in order to delineate the specific pinning mechanism of carbon. Carbon concentration, grain size, temperature, and strain rate were varied so that thermal-activation analysis and the Hall-Petch analysis could be used to evaluate the pinning mechanism. Cobalt was added to lower stacking fault energy so that the number and extension of split, screw dislocations would be increased in order to test the possibility of pinning by carbon at extended screw dislocations. EXPERIMENTAL PROCEDURE Nickel and cobalt (both 99.98 pct-. pure) were melted with graphite in stabilized zirconia crucibles and cast at lo-' Torr to form Ni-C and Ni-60 pctCo-C alloys. Two ingots were heated to 1250°C and were forged to 1-in.-sq bars. These bars were machined to 4-in.-round bars, and then swaged cold to 0.144-in. -diam rods. Reductions in area of approximately 75pct were used with intermediate anneals at 900°C for 1 hr. The carbon content of batches of 0.144-in.-diam rods from each ingot was reduced to two levels by annealing 5-in. lengths in palladium-purified, dry hydrogen at 1100°C for 25 and 100 hr. The remaining material from each ingot was annealed at 10"5 Torr for 1 hr at 1100"~. These treatments gave a total of three carbon levels for both the nickel and the Ni-60 pct Co alloy. The 0.144-in.-diam rods were swaged to 70-mil wire, cut into test specimens, and then re crystallized at lom5 Torr in capsules for 1 hr at temperatures ranging from 760" to 1050" ~. The capsules were broken and the specimens were immediately quenched into water. Average grain size was measured using Hilliard's method of circular intercepts." Annealing twin boundary intercepts were counted in addition to grain boundary intercepts to establish an average grain size. Average grain sizes ranged from 5 to 140 p depending on the cobalt concentration and re-crystallization temperature. Tension tests were made in duplicate at various temperatures at a crosshead speed of 8.34 x 10"4 in. per sec with an Instron Universal Testing Machine. Specimens of 1-in. gage length with soldered ball ends were used at atmospheric and cryogenic temperatures. Pinch grips were used on specimens at elevated tem-

Jan 1, 1969

By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

J. D. Fast and J. L. Meijering (Philips Research Laboratories, N. V. Philips' Gloeilampenfabrieken, Eindhoven, Netherlands)— After the departure of our friend Dijkstra to the United States, investigations on the effect of alloying elements on the behavior of nitrogen in a iron were continued in Eindhoven. We too found internal friction curves with two separate peaks for iron containing nitrogen in addition to 0.5 atomic pct V or 0.5 atomic pct Mo. Our first publication on these investigations" appeared almost simultaneously with the paper now under discussion. At first sight our experimental results seem to be in harmony with their conclusions, but a closer examination reveals that in the case of the Fe-V-N alloy the abnormal peak is not controlled by one time of relaxation only. Whereas iron containing 0.5 atomic pct Mn or Mo absorbs an amount of nitrogen of about the same magnitude as that absorbed by pure iron under identical conditions, iron containing vanadium absorbs in addition one nitrogen atom for every vanadium atom. This last amount, far exceeding the first amount in the case under consideration, combines chemically with the vanadium and causes no internal friction. The "free" nitrogen in the vanadium alloy gives rise not only to a damping peak corresponding to that in pure iron but— due to the presence of VN particles in the metal—also to the abnormal peak at higher temperatures. The VN particles create interstitial sites around themselves where the free nitrogen atoms are bound much tighter than in the normal interstices. These abnormal interstices, therefore, will capture free nitrogen atoms rapidly, whereupon these give rise to the abnormal damping. The binding energy in the abnormal interstices is not the same for all, and with coarsening of the VN precipitate the distribution of these energies is displaced toward the side of stronger binding. This is deduced from a shift of the summit of the second peak toward higher temperatures (from 80" to 88°C in our experiments) caused by prolonged heating at 950°C. From the intermediate state where they cause the abnormal damping, the nitrogen atoms pass over rather rapidly into the fully precipitated state (iron

Jan 1, 1954

By Van H. Manning

In substance, the international aspects of the petroleum industry, as these relate to the United States, are as follows: The domestic production is not keeping pace with the domestic demands; our best engineering talent warns us of the imminence of a decreased production by our oil wells, although more oil is needed; and the only practical source whence this increasing demand can be supplied for some time to come will be the foreign fields. Other nations have given thought to the future and, in recent years, have shown a tendency to adopt strong nationalistic policies regarding their petroleum resources, policies that hinder or prevent the exploitation of these resources by other nationals. In consequence, we find that, facing a probable shortage of the domestic supply, our nationals are excluded from foreign fields; and this in spite of the fact that foreign nationals have been permitted to enter into and exploit our own oil resources on an equality with American citizens and without hindrance or restrictions. This country has supplied the larger part of the petroleum consumed by the world and yet, with a failing supply imminent, it finds that those countries that, have been drawing upon our resources to supply their needs are showing a tendency to exclude us from their resources. In this way we shall be transferred from a position of dominence to one of dependence; and only by sufferance of those countries that are now seeking financial or political control of petroleum supplies, shall we be able to obtain the oil we will need. Impoetance of Petroleum Petroleum has become, during recent years, one of the essentials of our social and industrial life. All civilized countries recognize that the world is dependent on petroleum as on nothing else except textiles: foodstuffs, coal, and iron. Today, the tendency is toward an ever-increasing consumption of petroleum and its products as new and more efficient uses are found for them. The utilization of petroleum is extending more and more into the structure of our civilization. Consequently,

Jan 1, 1921

By D. M. Collingwood

The year 1928 has been marked by scattered but considerable wildcat drilling considering the overproduction prevalent in the oil industry. This wildcatting has resulted in the discovery of oil in one interior salt dome, several small fields producing from serpentine, Taylor marl, and Austin chalk, and two new fields producing from the Edwards limestone, one of which in the Bruner or Salt Flat area of Caldwell County promises to be of major importance if not quite as large as the Luling field. Fig. 1 shows production by fields for 1928, compared in the case of the older fields, with that for 1927. New Production From Salt Domes Boggy Creek Dome This salt dome was discovered in 1927 by core drilling and deep tests recommended on the evidence of surface geology. A large block of acreage controlled by the Humble Oil & Refining Co. covers the dome. Since the discovery of the deep-lying salt plug and oil on the flank of this dome in 1927, development has proceeded slowly. Since most of the acreage is controlled in a large block by one company there has been no intensive competitive drilling. Approximately 8 producers and 16 dry holes have been drilled. Production is from the eastern equivalent of the Woodbine and Eagleford horizons of the Mexia district, and has been found extending in a northeast-southnlest direction across the River Neches on the southeast flank of the dome. One of the best wells, the T. H. Jones No. 2, had an initial production of 90 bbl. per hr., and others have made from 100 bbl. per day to 50 bbl. per hr., but production of the better wells has either been shut in or choked down to less than 2000 bbl. per day. At the end of the year the daily average, production was about 2500 bbl. from 8 wells. Considerable gas pressure is present and one well, the Elliot Clark No. 2, drilled in 1927, was shut in with an estimated wet gas production of over 5,000,000 cubic feet.

Jan 1, 1929

By AIME AIME

A MODERN copper reduction works has both a genera1 chemical laboratory for control work and a research laboratory for the study of improvement of present processes and better working-up of by-products. The division of work in the general laboratory would naturally differ in different plants. The following statement to the writer from a chemist in one of the works will give a good idea of the type. of work in the general laboratory :

Jan 1, 1929

By F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760° C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove.

Jan 1, 1932

THE Johnson award for 1926 was given to T. L. Joseph for his experimental work on blast-furnace operation. When the Bureau of Mines undertook its experimental blast-furnace investigation in 1919, a number of operators and metallurgists were doubtful as to the practicability of small-scale tests. Several pre-vious attempts, outside the Bureau, to operate small furnaces had been unsuccessful. However, pig iron was produced in three and four-ton furnaces during the first half of the nineteenth century. The operation of a small furnace did not therefore seem an impossible task. This point of view, together with a realization of the importance of problems connected with the pro-duction of pig iron, prompted the Bureau to undertake this work. Such problems as the feasibility of using charcoal briquets as a fuel, the application of oxygen enriched blast, and the use of new ores and raw ma-terials, in general, can be investigated only at consider-able cost on full sized furnaces, while with an experimental furnace they can be conducted at a com-paratively ;small, cost. The results of small-scale tests are sufficient to determine whether the problem. War-rants the expenditure required for a trial on a com-mercial scale. The accompanying photographs and chart show the various stages of the experimental furnace development. Some idea of the size and shape of furnaces which were tested can be had from the development chart. In oper-ating furnaces A to F, a series of changes were made to increase hearth temperature. Perhaps the most im-portant change was the position of the tuyeres with respect to the bottom of the hearth. The height of the tuyeres above the hearth was gradually increased and the hearth diameter decreased. It was shown by this series of furnaces that metal and slag are the chief source of heat supply to the crucible. For this reason there is a minimum rate at which these materials can be brought into the hearth of a small furnace if it is to function properly. The rate of slag "and metal fall are determined by the burden on the furnace and the rate of blowing. Due to lack of funds necessary to provide ample blowing equipment, hot blast stoves, essential mechani-cal features, and to meet operating expenses, it. was necessary to work with much smaller furnaces, such as G to K shown in the chart. The particular object of these tests was to study the extent to which reactions could be speeded up by decreasing the size of the stock. One decided change, noticed at the beginning of this series of tests, was the effect which coke size had on the production of a strongly reducing gas. Furnace G, 22 in. high, operating on coke crushed to pass 10 mesh, made a gas richer in carbon monoxide than did fur-naces A to F, operating on run-of-the-oven coke.

Jan 3, 1927

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely, remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760° C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and sub-sequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove..

Jan 1, 1932

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By W. H. Blauvelt

The technical and engineering problems in the manufacture of coke are today the problems of the byproduct oven. Except in a few special localitics, practically no beehive ovens have been built in the United States for the last 5 or 6 years except as renewals of old plants, and during these years the total number of beehive ovens in existence has been steadily falling. On the other hand, the number of byproduct ovens has increased from 4624 in 1911 to a total of about 7660 in operation at the end of 1917; with 2800 building, this makes a total of about 10,460 which will be in operation in 1918, or shortly thereafter. Preliminary Government estimates place the total production of coke for 1917 at 56,600,000 tons, the largest tonnage in the history of the industry. Of this 34,000,000 tons, or 60 per cent., was beehive, and 22,-600,000 tons, or 40 per cent., was byproduct coke. Some time in 1918 the production of byproduct coke should pass the beehive output, and when the byproduct ovens now building are completed the total byproduct capacity will be about 40,000,000 tons of coke per annum, which is over 70 per cent. of the record-breaking total coke production of 1917. The reasons for these changes in the coking industry are familiar to all of us, and need not be discussed here. Improvement in Oven Design Since the byproduct oven was brought to this country from Europe, in 1892, it has been radically improved, and from the point of view of American metallurgical practice it is safe to say that the American ovens arc superior to those of Europe. The points of superiority are mainly those of larger units and larger output per unit, and the greater extent to which labor-saving machinery has been introduced. The increased output is largely due to the use of silica refractory material, which permits higher heats and shorter coking time than are employed in Europe. The modern American oven will carbonize commercially more than 20 tons of coal per day, and contrary to the European idea that slower

Jan 1, 1920

By M. O. Holowaty, C. M. Squarcy

1750 to 1850: The scene shifts westward across the Alleghenys to the young town of Pittsburgh; charcoal gives way to mineral coal as furnaces grow larger and the blast is heated; above all, Pennsylvania iron is adding strength to the new Nation and building an empire in the West. TWO names are inseparably associated with the Pittsburgh iron industry-those of George Anschutz and John Hayden. The iron ore deposits of southeastern Pennsylvania were found and developed early in the 18th century, and several forges and furnaces were built and operated. It was only after the revolution that the iron men crossed the Susquehanna River, built furnaces in the neighborhood of ore deposits of Franklin County, then along the Juniata River and its valley. Juniata Iron found a ready market in the Pittsburgh area. However, difficulty in transporting it across the Allegheny Mountains induced iron mas¬ters to seek ore and plant locations in the Pittsburgh district. One of the first to reach this area was George Anschutz, who migrated to America in 1789 at the age of 36, reaching Pittsburgh in the fall of 1790. Anschutz immediately set out to organize an iron company in Pittsburgh, and was able to interest some residents in his project. After being informed of an iron ore deposit located only three miles out of town (on the site of the present 26th St. and the Allegheny River) he decided to build there his blast furnace and foundry plant. Total cost of the installation was $300. When the furnace was put in operation, Anschutz, now known as Red George, found that the ore deposit was only an insignificant one and would last no more than a few weeks. A new deposit was found on Roaring Run, in the southeastern corner of Armstrong County. Anschutz transported some of this ore to the mouth of Two Mile Run, where it was loaded on horse wagons and transported to the furnace. In this way, he operated off and on for several months, until the furnace was blown out in 1794. After working for a year as plant manager for John Probst at Langhorntown, he built the Hunting-

Jan 1, 1961

By John C. Branner

Within a couple of years I have received many inquiries in regard to the manganese-mines of Brazil. These inquiries were doubtless directed to mc because I had lived and traveled in Brazil for more than eight years, and was therefore supposed to be pretty well acquainted with its geology and mineral resources. Somewhat to my chagrin, I not only knew nothing of manganese-mines in that country, but I had never before heard of the mineral having been found here in quantity, and I did not even know in what State the mines were located. The present summer found me in Brazil again, trying to finish up some of my early geological investigations along the northeast coast, and I have used the occasion to find out something about the manganese-deposits. Very little is known of these mines, even in Brazil. While at Pernambuco I was told that they were in the distant interior of the State of Bahia. In August I reached Bahia, and there I found out, concerning the mines and their geology, enough to be worth telling for the benefit of those interested in the mining or using of this mineral. Thus far, all the manganese-ore shipped from this State has come from two mines, the principal one of which is known as the Pedras Pretas mine. This was the first mine opened, is the best developed, and was the original discovery; the second one is on an adjoining tract, and the general geology and natural conditions are about the same in both. The Pedras Pretas mine is on the Nazareth-Amargosa railway, twenty-six kilometers west of the town of Nazareth, which is on tide-water, at the head of navigation, and is reached from the city of Bahia by a small side-wheel steamer that runs across the bay of Bahia and up the Rio Jaguaripe

Jan 1, 1900

By Carl Belser

This paper summarizes the data on the oil-shale deposits of western Colorado, Utah and Wyoming. It is based on published reports by the U. S. Geological Survey, on the results of core drilling and sampling by the Bureau of Mines, on the drill cuttings from the Genera1 Petroleum well, on a recent unpublished report by the Geological Survey on the geology of Naval Oil-Shale Reserves No. I and No' 21 and from information supplied by geologists of private companies who have investigated the Green River formation. The paper also contains a revised estimate of the grade and tonnage of minable thicknesses of oil shale of western Colorado. Introduction The oil shales of the Green River formation of Colorado, Utah and Wyoming comprise an important natural resource for the production of synthetic liquid fuels. The oil shale in western Colorado generally is more amenable to exploitation, apparently richer, and probably more persistent than in Utah or Wyoming. Work is now being done by the Bureau of Mines near Rifle, Cola. to ascertain the best procedures for mining the oil shale, producing shale oil from the oil shale, and converting the oil into more salable products. As a part of this program, holes were drilled and cores were taken of the oil shale on Naval Oil-Shale Reserve No. I. In addi- tion, drill cuttings were obtained from a well drilled through the Green River formation by the General Petroleum Co. about 18 miles northerly of the Naval Oil-Shale Reserve. Geology During middle Eocene time a broad, shallow body of water, now called Uinta Lake, covered northwestern Colorado and east-central Utah; a similar lake, known as Gosiute Lake, was in southwestern Wyoming Each of these contemporary lakes was bounded by high hills; the drainage was to the south. The Green River formation was laid down as sediments in the bottoms of these lakes. It is 3000 ft thick and has been divided into the following four members:

Jan 1, 1949

By Charles Colcock Jones

In any discussion of this very large subject we are confronted at the outset with so many obstacles that at best only a fragmentary and rather disconnected presentation can be made of it, and my hope is that building from the few facts I have to offer a more complete knowledge may be secured. In the whole intermountain and Pacific Coast region, west of Pueblo, Col., and from Canada to Mexico, there is no production of pig iron, and steel production is confined to the manufacture of a small amount of open-hearth steel from scrap. When we consider the area, the resources, and the several centers of population, this condition seems anomalous, even in the face of every counter argument as to cheap water transportation, or other means of transport from the Atlantic Seaboard or from the iron and steel centers of the Middle West. This comatose condition, if such a term may be applied, is certainly not due to a lack of all the essential materials and factors for success in iron and steel smelting, but is rather, I think, due largely to the general fact that it is only within a comparatively few years that the centers of population on the Pacific Coast have attained a size that would entitle them to the position of distributing or freight centers, or that the "back country" has been enough built up to make it sufficiently interesting to the railroads to foster trade from the local centers to the interior points rather than seek to supply such local centers and the interior by a transcontinental haul. "Ore Supply Edwin C. Eckel, in his monumental work on Iron Ores, has but little to say concerning the Pacific Coast deposits. He mentions (p. 269) those of Minaret, Madera County, and the Eagle Mountains, Riverside County, Cal., "perhaps 50 to 100 million tons each;" the deposits in Shasta County, worked for the electric furnace on Pitt River; and

Jan 1, 1916

By Daniel Hanson

FoR most of their practical applications metals are required to withstand stresses of appreciable magnitude: indeed, it id because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances—or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939