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By Royal Jackman

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investiga-tions. The development of X-ray examination of minerals and improve-ment in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investi-gators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation.

Jan 1, 1933

By Herbert Clark Hoover, Lou Henry Hoover

DIFFERENT methods of parting gold from silver, and, on the other hand, silver from gold, were discussed in the last book; also the separation of copper from the latter and further, of lead from gold as well as from silver ; and, lastly, the methods for refining the two precious metals. Now I will speak of the methods by which silver must be separated from copper, and likewise from iron.1 The officina, or the building necessary for the purposes and use of those who separate silver from copper, is constructed in this manner. First, four long walls are built, of which the first, which is parallel with the bank of a stream, and the second, are both two hundred and sixty-four feet long. The second, however, stops at one hundred and fifty-one feet, and after, as it were, a break for a length of twenty-four feet, it continues again until it is of a length equal to the first wall. The third wall is one hundred and twenty feet long, starting at a point opposite the sixty-seventh foot of the other walls, and reaching to their one hundred and eighty-sixth foot.

Jan 1, 1950

By R. M. Brick

THE etched microstructures of cold-worked alpha brasses, after reduc-tions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonomously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {111}, in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson5 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into sym-metry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By R. W. Powers, M. V. Doyle

ThE solution of a diatomic gas such as 0, or N2 in a metal usually follows Sieverts' law; i. e., Here C is the solute concentration at equilibrium and P, the gas pressure. The proportionality constant Ks is also the equilibrium constant for the reaction 1/2 02 (at pressure, P) - 0 (in solution at [21 concentration., C). to use oxygen as an illustrative gas. Sieverts' law is therefore interpreted to indicate that diatomic gases go into metallic solution atomically and that the solute "gas" atoms interact negligibly with each other. Of course, this interpretation is strictly valid only over the temperature interval in which the reaction indicated in [Z] can be investigated. At temperatures several hundreds of degrees below this interval, the possibility of interactions between solute atoms is conceivable. Indeed, from internal-friction measurements some evidence for the existence of groupings of oxygen atoms in tantalum solid solutions was presented a few years ago.1,2 Over a range of solute concentration, the experimental oxygen internal-friction peak in tantalum, measured as a function of temperature at constant frequency of vibration, can be described as the sum of two elemental peaks, each corresponding to a separate relaxation process. At 0.7 cps, the height of the elemental peak found at 137°C is proportional to the oxygen content, whereas the height of the one at 162°C varies as the square of the oxygen concentration. The 137°C peak was presumed to arise from the stress-induced ordering of oxygen atoms among various classes of octahedral sites in the manner proposed by Snoek.3 The 162°C peak was attributed to a somewhat similar stress-induced ordering process, in which each oxygen atom was interacting with a neighboring oxygen atom. Similarly, the experimental peak due to nitrogen in tantalum can also be described as the sum of two peaks. The height of one varies as the nitrogen concentration and the other as the square of this quantity. In fact, some evidence of solute interactions exist for all oxygen and nitrogen solid solutions of Group V transition metals. However, the interaction energy was not obtained previously for any alloy. The determination of this quantity, as a part of a more intensive study of the interaction between oxygen atoms in solid solution in tantalum, is reported in this paper. PRINCIPLE OF THE EXPERIMENT Consider an equilibrium in a solid solution of tantalum between oxygen atoms which are bound together pairwise and those solute oxygen atoms which are not so associated. 20 (Ta) - O2 (Ta) [3]

Jan 1, 1960

By F. J. Plecity, J. T. Michalak, W. C. Leslie

Isothermal recrystallization and grain growth in zone- and vacuum-melted irons and Fe-Mn alloys, up to 0.60 pct Mn, were studied in the range 480° to 650° C, after 60 pct cold reduction. In initial stages, rate of grain growth and rate of recrystallization of iron decrease with time. The recrystallization is typical of a growth-controlled process, and rate of growth is determined by the extent of recovery. Mn decreases rates of growth and of recrystallizatzon. The recrystallization process changes at about 0.30 pct Mn and nucleation may become time-depetzdet~t. In recent years, considerable effort has been expended in determining the effects of solute elements on recrystallization and boundary migration in fcc metals. The results have indicated that the effects produced by single solute additions are dependent upon both the element added and its concentration.'-' In contrast, there have been very few attempts to determine the characteristics of recrystallization and boundary migration in high-purity bcc metals, especially after heavy deformation, and the effects thereon of single solute elements.9-11 This study was undertaken to determine the recrystallization characteristics of various "high-purity" irons and the effects of manganese additions at two levels of base purity. It was hoped that the information obtained would improve our understanding of the recrystallization of pure metals and aid in formulating a theory for the effect of solute elements. The interest was not entirely academic, for the annealing of low-carbon steels, which is of very great commercial importance, is but poorly understood. MATERIALS The compositions of the irons and iron-manganese alloys used are listed in Table I. The zone-melted iron and Fe-Mn alloys were made by Battelle Memorial Institute. Iron S-1 was arc-melted in a water-cooled steel mold in an argon atmosphere. The ingot was forged into a bar, then given two horizontal zone-refining passes in an alumina boat. Iron V-4 was treated in a similar manner, but was not zone-refined. The iron for the zone-melted Fe-Mn alloys was induction melted in vacuum in MgO crucibles and cast into alumina molds. The ingots were forged into bars, machined to shape, and a groove milled down one side of each. The best available electrolytic Mn was placed in the grooves, and the bars were zone melted. The vacuum-melted Fe-Mn alloys were induction melted in this Laboratory in MgO crucibles and poured into cast-iron molds. Iron V-5 was purchased from National Research Corp. in the form of a small vacuum-cast ingot. The low-carbon steel was made by induction melting in air at the U.S. Steel Corp. Applied Research Laboratory. The history of the materials prior to the final cold reduction differed; these details are given in the Appendix. The penultimate grain size of the principal materials was kept in the range ASTM 2 to 4, except for the low-carbon steel. PROCEDURES The cold work prior to the final recrystallization anneal was kept constant at 60 pct. It is known that rolling procedure can influence the kinetics of recrystallization of ironI2; therefore, all specimens were rolled in one direction only, between clean,

Jan 1, 1962

By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By T. E. Davidson, C. G. Homan

This report deals with a study of the effects of extreme hydrostatic pressure on a polycrystalline material which exhibits a high degree of elastic anisotropy. Metallographically prepared polycrystalline bismuth samples were subjected to pressure levels up to 20,000 atm in a piston type gas-liquid system. The observed structural changes consisted of deformation localized along the grain boundaries, which appears to be a boundary migration phenomena, and widespread slip and cross slip. Subsequent deformation is progressive with increased pressure, and is substantially different in type from the deformation characteristic of uniaxial compression. A large amount of interest has been shown in recent years in the effects of extreme pressure on metals. In this connection, many investigations into the effects of pressure on physical and mechanical properties and reactions have been undertaken. Due primarily to the experimental difficulties involved, there has not been a great deal of study of the structural changes resulting from exposure of metals to extreme pressure. It has been difficult, for instance, to produce a true hydrostatic stress state in many of the extreme pressure devices used, and also to directly examine specimens metallographically before and after pressurization. The results of a preliminary investigation into one of the effects of extreme pressure, and its associated true hydrostatic stress state, on the structure of metals are discussed herein. Metals exhibit varied degrees of anisotropy in their physical and mechanical properties. Significant among the anisotropic properties is the modulus of elasticity, which varies by a factor of as much as three in some of the fcc metals, and by much larger factors in some of the less symmetrical elements. As a result of the variation of the modulus of elasticity with crystallographic direction, shear stresses will be induced in polycrystalline samples under true hydrostatic compression. Depending on several factors, these shear stresses could become of suffi- cient magnitude to cause localized plastic deformation. Presented herein are some of the structural changes observed in polycrystalline bismuth as a result of exposure to hydrostatic pressures of up to 20,000 atm. Although several other materials in both bicrystal and polycrystalline form are also currently under investigation, bismuth was chosen initially, due to its low symmetry and moderately high degree of anisotropy in the elastic properties. The fact that extreme hydrostatic pressure can induce structural changes in some elements in the polycrystalline state is of importance in itself. However, it may also be a factor in many of the other extreme pressure effects. For instance, this localized plastic deformation could substantially lower the recrystallization temperature, thus altering the effects of extreme pressure on this phenomenon. Also, as commented on by ridgman,' the hysteresis in the polymorphic transition of polycrystalline bismuth under extreme pressures could possibly be attributed to structural changes brought about by unequal compressibility. Therefore, to accurately determine the true effects of extreme pressure on metallic substances, one first must determine if any structural changes due to hydrostatic compression are also simultaneously occurring. The purpose of this work has been to determine whether the shear stresses induced by hydrostatic pressure in an anisotropic polycrystalline material, such as bismuth, could reach a magnitude great enough to cause plastic deformation and to study the resultant structural changes and effects. THEORY In a metallic crystal, the elastic properties are dependent upon the crystallographic direction and plane. Depending upon the degree of anisotropy of the elastic properties and other factors, internal shear stresses of sufficient magnitude to cause localized plastic deformation may be induced in polycrystalline material by true hydrostatic compression. The following highly simplified two-dimensional model of two adjacent grains in a polycrystalline aggregate under hydrostatic pressure serves to schematically demonstrate how these shear stresses arise in an anisotropic material.

Jan 1, 1963

By Norman Braly

THE following is not offered as an extended paper on the subject of shaft sinking, but more as a description of the present practice of shaft sinking in the Butte district. The Anaconda company is sinking at present the following shafts: Badger State, Moose, Mountain Consolidated, Mountain View, Pennsyl-ania and Tropic. At the High Ore and Leonard mines the shafts are being deepened by sinking two compartments and will subsequently be enlarged to the full working size by raising alongside the compartments which are now being sunk. The following other companies are also sinking shafts: Butte-Alex Scott, Butte and Zenith City, Boston and Corbin, North Butte Mining Co. (at the Granite Mountain shaft), East Butte Co. (at the Pittsmont shaft), and the Rainbow Lode Development Co. Shaft Timbering. The shafts of the Butte district, generally speaking, are of three compartments arranged in a straight line, and the pump compartment is usually arranged for the use of an auxiliary hoisting cage, as well as for carrying pipe lines and electric wires. The Rainbow shaft is practically square, and of three compartments. The length of the shafts outside of timber will vary from 17 to 22 ft., and the width from 6 ft. 6 in. to 7 ft. Fir timber is used in all shaft work. This may be obtained from the Coast, when it is known as Coast fir, or from Idaho or Montana, when it is known as native fir. The native fir seems to be the tougher wood, but it is hard to obtain clear lumber in the lengths and sizes necessary for shaft work. Some of the shaft timber of the Anaconda company has been treated with creosote as a preservative, but this practice has not come into general use, as the ground of the camp is so heavy that the timbers usually crush before they rot. The size of timber most .used for shaft work is 12 by 12 in., while 10 by 12 in., 10 by 14 in. and 12 by 14 in. are used for some of the special pieces around the shaft. The new Leonard shaft is timbered with 14 by 14 in. wall plates throughout.

Jan 8, 1913

By Cyrus Garnsey

NECESSITY FOR PRICE FIXING DURING the latter part of 1916 and the early months of 1917, clue to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to 82 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and so much complaint, that some action to regulate prices was considered essential by the National Administration. LANE-PEABODY AGREEMENT In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly-stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 9, 1918

By C. D. Thompson, D. C. Violetta, C. A. Czako

The mechanics of the continuous sintering process are briefly reviewed and the application of this process for the beneficiation of principal minerals used in making cement is shown. Pilot plant tests using pyrobeneficiation techniques were conducted with mixtures of limestone and shale in various ratios. Results are illustrated and show the percentage removal of carbon, carbonates, sulfur, alkalies, and volatiles as a function of the limestone-shale ratio. Tests with varying quantities of solid fwls, added to mixtures containing limestone and shale in a 4 to 1 ratio, were made to attain optimum elimination of the volatile constituents. Experimental results show that 90 pct of these constituents were removed during the calcination sintem'ng process. The advantages of using the beneficiated material for making cement are discussed with regard to prepam'ng, handling, and clinkering operations. A sintering process for treating raw materials or kiln waste products which contain high amounts of alkaline materials is described. Tests were performed with a high alkaline waste dust mixed in a 1 to 1 ratio with raw cement meal. The data from these tests and others using different halides for aiding alkali removal are evaluated by the alkali content of the cement clinker. Test results showed that the Dwight-Lloyd process could be applied with facility in beneficiating raw materials for cement making. Substantial quantities of deleterious volutile constituents were removed by calcining and sintering techniques. The continuous sintering process has been applied for a number of years as a means of beneficiating minerals for subsequent conversion to merchantable products. The process was developed and first used for nonferrous metallurgical applicatfons. However, it has risen to prominence for ferrous metallurgical applications where last year in the U.S. and Canada nearly 40 million tons of iron ore were treated by grate firing processes. Through the years of process development many investigators have realized the versatility of the sintering process and have directed experiments toward the use of it for applications with nonmetallic minerals. These have included calcining limestone, carbonizing coal, expanding shale, and burning cement raw meal. Today commercial sintering plants produce cement clinker from mixtures of limestone and shale, lightweight aggregate from shale or clay, and calcined products from phosphate shale. The mechanics of the downdraft sintering process have been presented by many authors. In general practice the materials to be agglomated are mixed as moistened fines with a solid fuel and this mixture is spread uniformly on the grates of the sintering machine. The charge is then momentarily directed under an ignition furnace. After ignition a continuous downdraft of air promotes combustion of the fuel and through heat transfer particles become partially fused into a coherent mass. This is cooled from continued draft induced after combustion. Many investigators have shown that distinct zones are formed during the process of sintering iron ores. At the midway point of the sintering process these are prominent and are, respectively, from the top of the bed to the bottom, comprised of a cooling zone of sintered material, a combustion zone of sinter formation, a calcination zone, a drying zone, and a zone of unreacted materials. Completion of sintering occurs near the discharge end of the machine where the firing zone approaches either the grates or grate dressing material called hearth layer. Here the peak draft temperature usually can be noted in the windboxes. The zonal pattern has been illustrated with the use of graphs which show thermal gradients as they progress through the bed of materials during sintering. Fig. 1 shows, in simplified form, thermal gradients existing when clinkering cement on a sintering machine. The thermal gradients illustrated are for periods of initiation, midway and completion of the clinkering process. The occurrence of these zones has importance for the beneficiation of cement raw materials. A research program was performed at the Dwight-

Jan 1, 1961

By R. D. Pehlke, P. D. Goodell, R. W. Dunlap

The rate of dissolution of steel bars in molten pig iron has been measured experimentally in the temperature range 2300° to 2650° F. The rate of solution is shown to be a .function of bath composition, temperature, and stirring. A kinetic model based on carbon diffusion in the liquid phase has been derived to fit the experimental results. THE rate of scrap melting has long been an important variable in steelmaking operations. With the advent of the oxygen steelmaking process and the accompanying shorter heat times, the rate of scrap melting has now become one of the rate-limiting factors in steel production. As observed in commercial practice, the solution rate is influenced by the compositions of liquid and solid, the temperature, agitation, and time. However, no definitive work has been done on the Fe-C system, and there is very little information in the literature regarding the relative effects of these variables in steelmaking systems. A number of questions have been raised in regard to scrap utilization in basic oxygen steelmaking operations. Consideration has been given to the optimum size and shape of scrap, and to the use of preheated scrap as a means for decreasing the pig-iron requirement in oxygen blowing. The determination of an optimum scrap practice for a specific installation depends to a large extent upon the economics of the scrap market and also upon the behavior of scrap in the vessel. The present research was undertaken as a preliminary study in evaluating the behavior of steel in a pig-iron bath under various conditions of temperature, composition, and agitation, as might be encountered in oxygen converter operations or in any steelmaking operation where scrap behavior is an important process variable. Related studies have been carried out on non-ferrous systems. The solution rate of solid aluminum in a molten A1-Si alloy has been studied.' Furthermore, the increasing use of liquid metals has created considerable interest in studies related to dissolution of a solid in a liquid, or mass transfer taking place between a solid interface and a liquid metallic phase.2-10 In an effort to clarify the relative importance of factors influencing the dissolution of scrap in Fe-C alloys, this paper presents the results of a study of the rate of dissolution of a low-carbon steel cylinder in a molten Fe-C bath at various bath compositions, temperatures, and conditions of agitation. An attempt has been made to determine the mechanism of solution, and a model has been derived to fit the experimental results. The rate of heat transfer between the molten pig-iron bath and the solid-steel cylinder has also been studied. EXPERIMENTAL PROCEDURE A molten bath of pig iron (nominal composition 4.2 pct C, 0.5 pct Mn, 0.8 pct Si)* was held in a 200- *In view of the fact that the composition of the pig-iron bath was slowly changing with time because of steel dissolution and reaction with the surrounding atmosphere, intermittent samples of the liquid bath were taken throughout each experiment, Table 1. lb induction melting unit. The internal diameter of the furnace was 8-1/2 in. and the bath depth approximately 14 in. Cold-finished 1020 steel cylinders of 1/2-, 3/4-, 1-, 1-1/2-, and 2-in. diameters were cut into 1 -ft lengths for use as test specimens. One end of each bar was machined to fit a hand-driven, mechanical stirring device which rested on top of the furnace. This fixture permitted 7 to 8 in. of the bar to be immersed in the melt. The steel cylinders were cleaned to free the surface of grease and oxide. The rods, at ambient temperature, were immersed into the molten pig-iron bath. The melt temperatures studied in this investigation were 2300°, 2500°, and 2650°F. Different agitation conditions were achieved by operating with a) the power to the furnace, giving induction stirring; b) induction stirring plus mechanical stirring, using hand rotation with a chain and sprocket assembly at approximately 200 rpm; c) mechanical stirring alone with the power off; and d) the power off and no mechanical stirring resulting in minimum agitation, i.e., only that caused by natural convection currents in the bath. The samples were immersed in the melt for prescribed times ranging from 30 sec up to 6 min. Immersion times were measured with a stopwatch and temperature control of the melt was achieved by power adjustment following temperature measurement with an optical pyrometer. The measurements with the calibrated pyrometer were checked out to within less than 10°F with simultaneous thermocouple measurements. Following immersion, the bars were water-quenched and the diameters were measured with a micrometer at several positions on the reduced area, and by volumetric displacement. The dissolution rates calculated from the

Jan 1, 1965

By John Griffen

THEORY HYDRAULIC classification as explained by Rittinger and others was largely restricted to conditions wherein the free-falling velocities of the particles were conceived as governing the separations effected (see chapter 9). The laws governing classification under free-falling conditions have been summarized by Chapman and Mott as fo1lows:l Nomenclature r represents, in a particle of irregular shape, the round-hole screen through which the particle would pass, or some other linear dimension of the particle equivalent to d, the diameter of a sphere. s, the specific gravity of the particle. 1, the specific gravity of the water used as a medium. K, a constant. W, the velocity of the water. In an Upward Current of water 1. A particle will move upward if [V > K dr(s - 1)] and, by suit- ably regulating the speed of the water current, the larger and heavier particles may be made to fall downward against the current, leaving the smaller, lighter particles in suspension in the current. 2. Particles such that [- = -] cannot be separated in an upward- current classifier with any one velocity of current. Coal particles having a specific gravity of 1.35 cannot be separated from refuse particles of [2.5 - 1 2.5 sp. gr.] unless the ratio of diameters is less than [ 4.3 to 1, 1.35 – 1] and the raw coal must be screened to size limits within this ratio if they are to be separated. Cone-shaped vessels or vessels of other shapes that allow the use of different velocities of current at different points in the flow are used to modify this limitation.

Jan 1, 1943

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By Thomas L. Garrard, James A. Sprague, Rex B. McLellan, Samuel J. Horowitz

A simple rnodel for interstitial solid solutions has been devised in which each solute atom interacts with the solzlent lattice in such a way as to exclude an integral number of nearest-neighbor sites from being occupied by solute atoms. The vemaining interstitial sites ave not affected. In calculating the entropy of such a solution the increase in the number of interstitial sites available to solute atoms due to the ozlerlap of blocked sites is taken into account. The ther-modynamic functions and the solute activity fov the solution rnodel are calculated. It is shown that considevation of the overlap sues vise to a correction term of the order 8' ( where 0 is the ratio of solute to solvent atoms) in the thevmodynamic functions of the solution and the solute activity. The theo,uetical equation for the solute activity was used to analyze the available data for the activity of carbon in austenite at three different temperatures. The use of a computer enabled many comparisons to be made between the experimental activity data and those predicted by both the complex blocking model and the simple, widely used blocking model in which the ozierlapping of blocked sites is not taken into consideration. Even though at the highest concentvations oj carbon the value of 0 is small it is shown that the best fit to the experimental data is found with the complex blocking model. RECENTLY it has been shown by analysis of gas-solid equilibriums that many interstitial solid solutions can be described by the quasi-regular solution model in which the partial energy of solution E, is independent of composition and, apart from a composition-independent term due to nonconfigurational factors, the partial entropy is that of an ideal solution. Dilute solutions of nitrogen in both bcc and fcc iron,' dilute solutions of oxygen and silver,' carbon in a Fe,' and dilute solutions of carbon in ? Fe2 are all quasi-regular. In addition many hydrogen-metal solutions, both dilute and concentrated (with the notable exceptions of the H-Ni and H-Pd systems), can be described by this model.3 However, it has been shown that, at various temperatures, solutions of carbon in ? Fe begin to depart strongly from quasi-regular behavior at low concentrations. A plot of the activity of carbon in ? Fe relative to pure graphite vs atom fraction of carbon (Cc) calculated from Smith's data4 begins to depart from the (nonlinear) plot for a quasi-regular solution at about Cc = 0.02. Several statistical models have been proposed to account for the thermodynamic behavior of carbon in y Fe. Darken and smith4 set up a model in which a carbon atom in its octahedral site in the fcc lattice has either one or no neighboring carbon atoms in the twelve nearest-neighbor octahedral sites. It is assumed that the number of carbon atoms having more than one nearest neighbor is negligibly small and that a solute atom does not interact with another solute atom located at a greater distance than the first shell of interstitial sites. Thus this model contains two characteristic interaction energies. Darken and Smith showed that this model gives reasonable agreement with the measured variation of carbon activity ac with composition. It is noteworthy that Darken and Smith concluded from their analysis of the activity data using this model that there was a repulsive force between carbon atoms in austenite which reduces the concentration of C-C pairs below that corresponding to random mixing. Recently Aaronson, Domian, and pound5 have considered in detail the statistical model developed by Lachere and by Fowler and Guggenheim7 and have shown that it is compatible with the activity data for carbon in austenite. In Darken's model the energy of solution of carbon in austenite is dependent on temperature and concentration; the departure from Henry's law arises from the concentration dependence of the energy of solution. In Aaronson, Domian, and Pound's discussion of the Lacher, Fowler, Guggenheim model the interaction energy wy between adjacent carbon atoms in austenite is strongly temperature-dependent. Aaronson et al . suggested that this temperature dependence of wy and hence the energy of solution of carbon could be explained either by the formation of clusters of carbon atoms (despite the repulsive nature of wy) or by the dual occupancy of the octahedral and tetrahedral sites by the carbon atoms. However, a temperature-dependent heat of solution

Jan 1, 1968

By C. H. Mathewson

(New York Meeting, February, 1916) DURING the past year considerable work dealing with the mechanical properties and microstructure following the anneal under uniform conditions of certain types of commercial rolled brass has been done in this laboratory. Since these experiments were conducted with the active cooperation of the Bridgeport Brass Co., involving free use of its product, and have thus furnished information which is characteristic of some of its special mixtures, full publication of the numerical relationships and comparative results encountered does not seem justifiable. Some of the more general features of this work are, however, available and it is our present purpose to use the material in question, along with some results of special tests, in discussing the characteristics of recrystallization as related to the degree of hardening by strain and the ordinary annealing variables. We desire to make acknowledgment of the many courtesies extended by Mr. Charles Ferry, Metallurgist of the Bridgeport Brass Co., and the value of his cooperation, which has greatly stimulated the study of brass in this laboratory. A clear and systematic presentation of the principal relations between temperature and time of anneal, the changing physical properties and microstructure and the degree of previous reduction by cold-rolling, was first made, in the case of rolled brass and copper, by the French engineer, C. Grard,1 in 1909, although much fragmentary information of this general character had appeared earlier and the main facts involved were undoubtedly known to many brass specialists through their own private research. From this work, it appears that in the cartridge mixture (67 per cent. copper, 33 per cent. zinc) the properties imparted by cold-working within the limits, 13 to 75 per cent. reduction of area by rolling

Jan 1, 1916

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By D. Harker, M. J. Murphy

The mechanism by which age-hardening takes .place is still not completely understood. The principal theories range from the extreme of "precipitaiion-hardening" to that of "order-hardening," with many intermediate gradations. In the hope of obtaining new data on which to base a choice among the many theories, the authors have made electron micrographs of formvar replicas taken from metallic specimens at various stages of age-hardening. The results so obtained on an alloy of 2 per cent beryllium in copper and one of 20 per cent molybdenum in iron will be described in the following pages, as well as the technique used in preparing the replicas. Preparation of Formvae. Replicas of Metallic Specimens This section is concerned with the techniques that have roved successful in preparing formvar replicas for studying the microstructure of metals with the electron microscope. Because of its simplicity and accuracy, the formvar replica1 method developed in the General Electric Research Laboratory has been used exclusively, since it is much simpler than the silica replica method of Heidenreich and Peck2 and produces as good results. The formvar method to be described requires a technique acquired only by practice, and no foolproof set of rules can be given. it is a rapid method and a replica can be obtained in less than five minutes under favorable conditions. This does not mean that perfect replicas can be produced every five minutes, but rather that one can well afford to take several strippings* in order to produce a replica of high quality. The metallographic technique required for replica work—very fine polishing and etching with very dilute solutions—is described here. It can be said, in general, that almost any surface that has been carefully prepared for a photomicrograph at 1000 or more diameters can be used to obtain a replica for the electron microscope. Preparation of Metallographic Specimens The preparation of the metallographic specimens is somewhat more exacting than that usually given to samples to be used for inspection under the light microscope. After much experimentation, it was concluded that the best method consists in polishing the metal through to the coarse cloth, then etching and repolishing on final cloth until the layer of distorted metal is removed. After this procedure has been completed, a dilute etch—to approximately the depth necessary for a micrograph at 1000 diameters—usually produces a sur-

Jan 1, 1945