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By M. C. Flemings, G. E. Nereo

General expressions are given to describe macro-segregation in castings and ingots which results from mass flow of solute-rich liquid to feed solidification and thermal contractions. Analytical solutions are given for solidification with planar isotherms (unidirectional and bidirectional heat flow). These solutions describe inverse segregation and centerline segregation. Numerical examples are given for A1-4.5 pct Cu alloy. In 1540, Vannoccio Biringuccio published one of the first references to macrosegregation, describing the problem of exudation and inverse segregation in the manufacture of bronze gun barrels.' Since then, a great many studies of macrosegregation have been reported. Recent work of particular engineering interest includes that of Marburg 2 and others:" on centerline segregation and other types of segregation in large steel ingots, and work of Adams,5 Scheil, 6 and Kirkaldy and youdelis7 on inverse segregation in nonferrous ingots. In most studies on this subject, the various types of macrosegregation have been treated as separate phenomena. For example, quite different mechanisms have been proposed for formation of centerline segregation, negative cone of segregation, inverse segregation, banding, and so forth. In this, and in several papers to follow, it is proposed that these as well as other types of macrosegregation result from the same basic mechanism and can be quantitatively described by the same basic equation. It has often been suggested that some types of segregation (such as centerline segregation and banding) occur as a result of buildup of solute at the tips of growing dendrites.2-4 ,8-10 As example, banding can be induced in centrifugal castings by mechanical vibration, and Northcott 10 suggests this might be due to the influence of the vibration on the boundary layer at the dendrite tips of the growing dendrites. However, in view of the extremely small boundary layer known to exist at the tips of the dendrites,11,12 any interpretation of macrosegregation based on this boundary layer is clearly incorrect. Note that experiment has shown that significant buildup of solute does not occur at dendrite tips in ingot solidification, but even if such buildup occurred the thickness of the enriched zone would only be the order of D/U where D is liquid diffusion coefficient and U is dendrite tip velocity. For usual casting or ingot solidification this solute-enriched layer is 10"3 cm, far too small to account, for example, for centerline segregation.11'12 It has also been suggested that convection in the bulk liquid (ahead of the advancing dendrites) might cause segregation by sweeping away the solute-rich boundary layer in front of the dendrites.3 However, since there is no significant boundary layer, this explanation must be incorrect. The convection might directly cause segregation by penetrating between the dendrite arms, and presumably in a rimming steel ingot it is sufficiently vigorous to cause some segregation in this way. Centerline segregation, however, cannot be interpreted as resulting from this convection since a sharply segregated zone is usually found near the centerline, with the bulk of the ingot being nearly of nominal composition. If convection in the bulk liquid were the direct cause, a gradual change in ingot composition over the entire cross section would be expected. It is known that sudden changes in convection of the bulk liquid during solidification can result in banding,14 but it is not clear that the banding results directly from the effect of convection on solute distribution. Changes in convection also affect thermal conditions in the liquid-solid region of a solidifying ingot. It will be seen later in this paper, and in a paper to follow, that macrosegregation is strongly influenced by these thermal changes. Recognizing that in some cases of ingot solidification (as in solidification of rimming steels) convection in the bulk liquid may have a direct effect on solute distribution, we neglect it in this paper and in the several to follow. We then derive general expressions describing macrosegregation which results from the mechanism of interdendritic flow of solute-rich liquid

Jan 1, 1968

By S. W. Kessler, R. B. Pond

Metal specimens were solidified through a measured thermal gradient so a free surface and the liquid-solid interface could be examined. A line structure was observed on the surface and a hexagonal structure on the interface. A model to explain these forms is proposed. NUMEROUS observations of the dendrite form have been made both in nonmetallic and metallic systems. From these, extrapolations have been made as to the probable dendrite form in pure metals. Observations of the dendrite form in pure metals, nevertheless, have been scanty. In general, these observations have been made on the skeleton dendrite after the mother liquid has been drained from around it, and a mechanism of the formation of the dendrite has been postulated from this solid form. Recent investigations have been conducted in an endeavor to make a study of the formation of the dendrite in several pure metals and the effect of several variables on this mechanism and final form. For these investigations, an apparatus was designed and constructed as shown in Fig. 1. It consists of a talc block containing a half-cylindrical depression, the end of which terminates in the conical recess of a copper block having an external attachment for cooling. A heating coil extends the length of the mold just beneath the lower limits of the cavity. The entire cavity for holding metal is coated with a thin film of graphite. Six thermocouples are equally spaced in the cavity and under the graphite, and six microammeters indicate the temperatures at the particular thermocouple stations. Readings were taken of all meters at the same instant time measurements were taken by photographing the panel of microammeters and a stop watch which was started at the beginning of the run. It was possible with this apparatus to solidify metals through a measured thermal gradient and to observe the progression of the liquid-solid interface with time by following the formation of the dendrite markings in the surface of the solid material. These

Jan 1, 1952

By Edwin Hopkins

THE year 1923 started a few days after the Venezuelan Oil Concessions, Ltd., discovered a 140,000-bbl. well at. La Rosa and a well of between 2500 and 5000 bbl. at La Paz, on the opposite side of Lake Maracaibo. These nearly simultaneous events changed, overnight, the general aspect of oil affairs in Venezuela. Up to that time, big things had been expected by the companies then in the district, but many major companies had shown little interest in the country. Within a few weeks the Pure Oil. Co. and the Gulf Oil Corpn. entered the field and acquired large properties. The Texas Co. purchased several concessions and the Standard of California, Atlantic Refining Co., and Mexican Petroleum Co. established offices. Representatives of many other companies visited the district during the first few months of the year. The sudden influx of buyers naturally caused a great rise in prices and this, together with overproduction in the United States, doubtless caused the slowing up of concession transfers in the latter part of the year. The following property transfers occurred: (1) The Gulf Oil Corpn. contract with the Maracaibo Oil Exploration Corpn., whereby the Gulf acquired the right to select 100,000 acres from the Maracaibo's zones. (2) The Gulf Co. purchase of one-quarter interest in seven concessions of the New England Oil Corpn., Ltd. (3) The Gulf Oil Corpn. purchase of several concessions of Kunhardt and others in the Perija district. (4) The Gulf Oil Corpn. purchase of certain portions of the one-kilometer Lake zone that were not covered by parcels or Government reserves (namely the "sobrantes"). (5) Pure Oil Co. purchase of all Government reserves turned back by Maracaibo Oil Exploration Corpn. in the districts of Mara and Miranda. (6) Standard Oil Co.: of New Jersey deal with the British Controlled Oilfields, Ltd., for control of approxi-mately the eastern third of the .district of Buchivacoa, state of Falcon. (7) Royal Dutch deal with the British Controlled Oilfields, Ltd., for the control of the central third of the district of Buchivacoa, Falcon. (8) The Texas Co. purchase of several concessions in Perija and one west of Mene Grande on the east side of Lake Maracaibo. (9) Purchase by the British Equatorial Oil Co., Ltd., of Goverment reserves corresponding to certain Creole Syndicate parcels under the margin of Lake Maracaibo near La Paz. (10) The Lago Petroleum Co. acquired a concession on all of Lake Maracaibo except a 1-Km. strip along the shore.

Jan 3, 1924

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By W. B. Gogarty

With the use of polymer solutions in secondary recovery operations, the need has developed to understand the mobility control mechanism. This study investigated mobility control by considering both permeability and rheological effects. Experiments used a high molecular weight, partially hydrolyzed polyacrylamide polymer. Flow studies took place in reservoir and Berea cores having zero oil saturation. Effective size of the polymer flow unit was inferred from Nuclepore filter tests. Clay studies indicated the particle size capable of decreasing the core permeability. Flushed permeabilities measured the approximate core permeabilities with flowing polymer solutions. These permeabilities were considerably lower than original values. With mobility data and the flushed permeability, maximum effective viscosities were determined for polymer solution flow in a core. Effective viscosities showed that rheological properties play an important part in mobility control with polymer solutions. The study showed that permeabilities decrease and stabilize with polymer flow. At the lower permeabilities, high shear rates exist in the cores. Because of the pseudoplastic character of the polymer solution, the high shear rates caused low effective viscosities. This condition pointed to the inefficient use of the potentially high viscosity of the polymer solution at low shear rates. INTRODUCTION In the oil industry, a great deal of interest is being shown in the use of polymer solutions for secondary recovery and a number of polymer floods are being performed in the United States.1 Some of these floods have become commercial while others have been reported as failures. A number of floods are still in progress and remain to be evaluated. With the advent of polymer flooding, the need developed to understand the mobility control mechanism in porous media. Rheologically, the polymer solutions behave as pseudoplastic fluids. Investigators have studied the rheology for this type of non-Newtonian fluid in porous media?-6 Results have also been reported on the ability of polymer solutions to decrease mobility.7-10 Some investigators indicated that polymer solutions show a different rheological behavior in cores than on the viscometer.7,8 This study is representative of an initiatory investigation on mobility control with polymer solutions. Some effects are considered on a qualitative basis. Mobility control is considered from the standpoint of both permeability and rheology and, to the extent possible, permeability and rheological effects are considered separately. Results show that mobility control occurs from a reduced permeability caused by polymer retention and an effective viscosity determined by the average shear rate in the core. In this respect, rheological behavior is as important in mobility control as permeability. PROCEDURES A high molecular weight, partially hydrolyzed, polyacrylamide polymer was used in the investigation. Solutions of various concentrations were made with this polymer in different types of water. Some solutions used distilled water and others used tap water. The tap water contained approximately 500 ppm dissolved solids. As used in this paper, concentrations in ppm refer to parts by weight solute to one million parts by weight of solvent. In the tap water, calcium and magnesium accounted for from 60 to 80 ppm of the solids, the remainder being mostly sodium chloride. All solutions contained a bactericide, and anti-oxidants and antiprecipitants were added to the tap water. Capillary and concentric-cylinder* viscometers determined the rheological properties of solutions. The capillary viscometer is described elsewhere.6 Berea and reservoir sandstone were used as core materials for this investigation. Cores were 1 in. in diameter by approximately 2 to 3 in. long. Prior to mounting, the Berea cores were heat-treated for 3 hours at 850F. This treatment decreased the water-sensitivity of the clays in the cores. The reservoir cores were cleaned with solvent and

By G. Derge, M. Bourgon, G. M. Pound

A STUDY of electrical conductance in molten Cu-Fe sulfide mattes' has shown that pure molten Cu,S behaves like a semi-conductor in that it is an electronic conductor and its specific conductance, of the order of 100 ohm-' cm-', increases with increase in temperature. On the other hand, pure molten FeS, another electronic conductor, behaves like a metallic conductor in that its specific conductance, about 1500 ohm-' cm-', decreases with increase in temperature. Molten solutions of Cu,S and FeS follow a roughly additive rule of mixtures with respect to both specific conductance and temperature coefficient. The behavior of molten Cu,S may be understood, by analogy to the situation in solids, in terms of semiconductor theory.' It is thought that, although the melt consists of cuprous and sulfide ions, the bond between these atoms has a certain degree of cova-lency. According to the simplest concept the electrons in the partially covalent bonds are thermally promoted to a conduction band. In another concept, small amounts of impurities (undetermined) provide donor or acceptor levels in the forbidden zone between the valence and conduction bands and thus facilitate semi-conduction in the usual way. However, the metallic behavior of molten FeS is difficult to explain, because one might expect from similar reasoning that it too should act like a semi-conductor. It was suggested that the apparent metallic behavior of molten FeS might be explained by a large negative temperature coefficient of density. Thus if molar conductance instead of specific conductance were plotted versus temperature, the slope might prove to be positive, indicating semi-conduction instead of apparent metallic conduction. Accordingly, density measurements were made in order to answer this question in regard to molten FeS and also to provide data for conversion of specific conductance to molar conductance for molten Cu,S and a molten 50-50 wt pct Cu-Fe sulfide matte. Experimental Diagrams of the apparatus are given in Figs. 1 and 2. A 3 x 8-cm dense alundum crucible containing the prefused specimen is positioned in the uniform temperature zone of an induction furnace tube and melted under a helium atmosphere. Then the cell assembly, consisting of two 3-mm spectro-graphite rods, one of which is in a 1-cm ID open

Jan 1, 1959

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates' have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By A. Josefsson

The transition temperatures of 0.01 to 0.02 pct carbon steels are shown to be strongly influenced by cooling rate in the a range, quenching from A, causing a very low transition temperature even after strain aging. In a titanium-stabilized steel and in a steel with 0.05 pct C this effect is absent. NORMAL mild structural steels usually show a structure of more or less pure ferrite, as a matrix, in which cementite grains or pearlite are embedded. Of these components, ferrite is by far the most interesting one as far as ductility and brittle (cleavage) fracture are concerned. Obviously, pear-lite and carbide are by no means necessary for a cleavage crack to nucleate and grow in the ferrite, as steels with a very low carbon content (Armco iron with 0.02 pct C) have an impact transition temperature just as high as semikilled steels with 0.26 pct C.1 Although it has been argued that a very embrittling effect is to be expected from cementite, precipitated as continuous films along the ferrite grain boundaries,'. " the micrographic evidence for a direct causal connection between the brittleness and these films does not seem to be very convincing. On the other hand, it has been stated that cementite particles in ferrite are able to stop ferrite cracks.4,5 In any case, the properties of the ferrite itself seem to be of overwhelming importance to the ductility of steels, justifying a thorough study of steels consisting of ferrite of different compositions, but principally free from pearlite, which means a carbon content below 0.02 pct. Such investigations have been carried out using the impact transition temperature as a criterion of the tendency to brittle fracture and have given some rather unexpected results. One result is the profound influence of carbon on the transition temperature of the steel in normalized condition. If the carbon content is reduced from 0.02 to 0.015 pct and below, a nearly discontinuous decrease in transition temperature appears even with high percentages of such elements as phosphorus and nitrogen present. This will be reported elsewhere." The present paper deals with another effect of carbon upon transition

Jan 1, 1955

By E. T. Turkdogan, B. B. Rice

Desulfurization of limestone during and subsequent to calcination has been investigated using U.S. Steel's Rogers City quarry-Michigan limestone cut to 25-30-mm diam spheroidal shapes. The experimental observations indicated that the sulfur present as iron pyrite in commercial limestone is oxidized partly to SO, during calcination and partly converted to sulfides (FeS, CaS) and CaSO4. If calcination is carried out under oxidizing conditions, most of the sulfur is converted to CaSO4, which can be removed from burnt lime readily in CO,-CO mixtures, the higher the CO content the faster is the rate of reaction. In the 30-mm-diam spheroids gas diffusion in the pores of limestone and burnt lime is fast relative to rates of the desulfurizing reactions. Over the temperature range investigated, e.g., 850° to 1200°C, there is internal desulfurization.

Jan 1, 1974

By W. C. Muehlhof, L. D. Lamont

THROUGHOUT the anthracite industry's history, the problem of handling and dis¬posing of refuse material has been one of major importance. In the early days of the industry's activities, only the large sizes of anthracite were satisfactory for market requirements and the smaller sizes were deposited as refuse. As time went by, more efficient coal-burning equipment was developed and a market demand was created for the finer sizes of coal. This demand made it possible to recover market¬able coal from banks deposited as refuse in the earlier days of mining. The same condition holds good today and we can see a definite trend toward the objective of utilizing the No. 4 and No. 5 buckwheat sizes. Under present conditions, we know that a limited market exists for No. 4 and 5 buckwheat; we know that the finer sizes of anthracite can be burned as pulverized fuel; we know that these fine sizes can be processed and sold as bri¬quettes, and we also know that the heat content of these fine sizes of coal is compar¬able with that of the sizes now merchan¬dized. Therefore, it should be the objective of the industry to conserve these fine sizes of coal in such manner that if and when processing facilities are developed, and market demands exist, the material can be salvaged and made available to meet these demands. From the standpoint of economical future reclamation, the ideal method of disposing of refuse containing the finer sizes of coal is to deposit it in banks separate and apart from other breaker refuse. By this procedure, the minimum amount of material will be processed in future salvage operations to recover the No. 4 and No. 5 buckwheat sizes. Many collieries in the anthracite region are operated under leases that have a specific term. These lease agreements provide that, upon expiration of the lease by term, exhaustion or otherwise, the ownership of the refuse material reverts to the lessor. Therefore, a question was raised in the minds of these operators: Why should I assume the expense of such pro¬cedure when I have no assurance that I will benefit by the future processing and sale of these fine sizes? Under present conditions, the answer to this question is not one of choice but of necessity, as restrictions imposed by legislation make it mandatory on operators of preparation plants to take necessary steps to properly treat silt-laden waters before permitting them to enter the streams. By reason of these restrictions, the disposal of fine sizes becomes a secondary_ rather than a primary operating con sideration, and the procedure for disposing of this refuse becomes a matter of choice governed principally by topographical and geographical conditions. METHODS OF HANDLING REFUSE There are three principal methods of handling and disposing of fine-size refuse; namely :

Jan 1, 1946

By B. H. Sage, W. N. Lacey, W. M. Morris

The volumetric behavior of isobutane at temperatures below its critical temperature has been studied by several investigators. Seibert and Burrelll measured the vapor pressure of isobutane from the ice point to the critical temperature. Dana and co-workers2 determined among other thermodynamic quantities the density of the saturated liquid and the saturated gas and the vapor pressure from approximately 0 to 130 F. Sage and Lacey3 studied a number of the thermodynamic properties of this hydrocarbon from 70" to 250" F. The specific volume in the gas and liquid region was determined at pressures up to 3000 Ib. per sq. in.? throughout this temperature interval. In addition, the vapor pressures were measured at 30" intervals. These data taken together serve to establish the thermodynamic behavior of isobutane at temperatures between 0" and 250" F. with reasonable accuracy. However, apparently there are no data available at the higher temperatures. For this reason an investigation of the volumetric behavior of isobutane at temperatures between 100" and 460" F. was carried out with apparatus that has been described in another paper (p. 136, this volume). Materials The isobutane used in this investigation was obtained from the Philgas Division of the Phillips Petroleum Co. That company's special analysis upon this sample indicated it to contain less than 0.03 mol per cent of impurities. In order to avoid traces of noncondensable gases, this hydrocarbon material was subjected to two successive fractionations at a high reflux ratio in a column approximately 4 ft. long and % in. in diameter, which was packed with small glass rings. The middle portion of distillate from the first fractionation was used in the second fraction-ation and a portion of the overhead from this second distillation process was repeatedly condensed at liquid-air temperatures at a pressure only slightly above the sublimation pressure of isobutane at this temperature.

Jan 1, 1940

By W. N. Lacey, B. H. Sage, W. M. Morris

The volumetric behavior of isobutane at temperatures below its critical temperature has been studied by several investigators. Seibert and Burrelll measured the vapor pressure of isobutane from the ice point to the critical temperature. Dana and co-workers2 determined among other thermodynamic quantities the density of the saturated liquid and the saturated gas and the vapor pressure from approximately 0 to 130 F. Sage and Lacey3 studied a number of the thermodynamic properties of this hydrocarbon from 70" to 250" F. The specific volume in the gas and liquid region was determined at pressures up to 3000 Ib. per sq. in.? throughout this temperature interval. In addition, the vapor pressures were measured at 30" intervals. These data taken together serve to establish the thermodynamic behavior of isobutane at temperatures between 0" and 250" F. with reasonable accuracy. However, apparently there are no data available at the higher temperatures. For this reason an investigation of the volumetric behavior of isobutane at temperatures between 100" and 460" F. was carried out with apparatus that has been described in another paper (p. 136, this volume). Materials The isobutane used in this investigation was obtained from the Philgas Division of the Phillips Petroleum Co. That company's special analysis upon this sample indicated it to contain less than 0.03 mol per cent of impurities. In order to avoid traces of noncondensable gases, this hydrocarbon material was subjected to two successive fractionations at a high reflux ratio in a column approximately 4 ft. long and % in. in diameter, which was packed with small glass rings. The middle portion of distillate from the first fractionation was used in the second fraction-ation and a portion of the overhead from this second distillation process was repeatedly condensed at liquid-air temperatures at a pressure only slightly above the sublimation pressure of isobutane at this temperature.

Jan 1, 1940

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By Robert P. Roberts

In order to obtain data on the thermal effect of the blast-furnace jacket and on the water consumption in these jackets a series of tests were run on the 56 by 180 in. blast furnaces at the Great Falls Reduction Department of the Anaconda Copper Mining Co., at Great Falls, Mont. The arrangement of the jacket is shown in the transverse section of one of the furnaces (Fig. 1) on which the tests were made. The nose, spout, and breast jackets have independent water supplies and discharges. The end and side jackets are connected in pairs, as regards water supply, the feed water entering at the bottom of the lower jacket and overflowing into the bottom of the jacket immediately above it, and discharging into an independent overflow pipe for each pair of jackets. Tests were run on the main side and end jackets, the breast jacket, the spout, and the nose. Measurements were taken of the quantity of water discharged per minute and the rise in temperature of the water in its passage through the jacket. The product of these two results, expressed in the proper units, evidently gives the number of units of heat removed per minute by the water. Sufficient work was done on each type of jacket to determine its behavior under different conditions, and the results from each set of conditions were checked by repeating the work from three to six times. The method used was as follows: The overflow from the jacket to be tested was arranged to discharge at will into a barrel, mounted upon platform scales. The discharge temperature was read just before turning the water into the barrel, and just before turning it back to the sluice; if the test lasted more than a minute, additional temperature readings were taken at 1-min. intervals from start to finish. The elapsed time of running the water into the barrel was determined with a stop-watch, and this figure, combined with the in-

Jan 1, 1914

By J. J. Gilman

Rates of prisnzatic plastic glide ( {1010}<2110>) in pure Cd crystals have been measured at temperatures from 158° to 276°C. The glide rate is proportional to the 2.75 power of the applied shear-stress. The activation energy is 29.2 kcal per mol. It is suggested that the rates of prismatic glide in Cd and Zn crystals are determined by the strengths of the atomic bonds across the prism planes. ALTHOUGH zinc and cadmium crystals both have hexagonal structures with nearly the same c/o ratios, their mechanical behaviors are quite different. Whereas zinc becomes quite brittle below room temperature, and cleaves readily on (0001) planes, cadmium is very ductile even at 4.2°K, and cannot be cleaved at any temperature. As part of a search for the explanation of this difference in behavior, a study has been made of prismatic glide in cadmium. It complements a previous study of the same phenomenon in zinc.1 The primary glide plane in cadmium is the basal (0001) plane, and the primary glide direction is the direction of atomic close-packing <2110>. However, if a tensile stress is applied parallel to the basal plane, then the shear stress on the basal plane equals zero so basal glide cannot occur. At low temperatures, deformation by twinning occurs; but at high temperatures, it has been found in this study that gliding on prismatic planes (1010) occurs in the close-packed direction. This is completely analogous with the case of zinc, except that lower temperatures are required. EXPERIMENTAL The experiments were done in nearly the same way as for zinc.&apos; Therefore, only the differences in the two sets of experiments will be described here; for other details the reader is referred to the previous paper. Crystals 6 by 6 mm sq were used that were grown from "Super Purity" 99.999 + pct Cd purchased from the New Jersey Zinc Co. The crystals were grown with their basal planes parallel to both the rod axis and one of the flat sides of the square cross section, A close-packed direction in the basal plane was oriented parallel to the rod axis. Gage sections were carefully machined into the crystals, and the surface damage caused by machining was removed with the same chemical polishing reagent as had been used for zinc. Thus, specimens of the same form and size as the previous zinc ones were produced. The crystals were heated to the test temperatures in a silicone oil bath (fused salts were tried first, but they reacted badly with the cadmium). An Instron tensile-testing machine was used for applying stresses to the crystals at various constant strain-rates. RESULTS The general behavior of cadmium crystals is much the same as for zinc. Only the constants that measure specific properties are different. Just as

Jan 1, 1962

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,&apos; and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6&apos;s viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG&apos;S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.&apos; Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By B. J. Reid, J. N. Greenwood

It has been shown1 that cavities are formed in the grain-boundaries of copper and 70:30 brass (as well as in magnesium) by the application of tensile stresses at elevated temperatures. For a given rate of strain, cavities are formed in brass at a lower temperature than in copper, and they are larger; it was thought that this earlier onset of cavitation in the alloy might be caused by the distortion produced in the metal lattice by the alloying element. If the cavitation is caused by the vacancy-migration mechanism, &apos; the distortion of the lattice would reduce the energy required for vacancy formation, and thus provide vacancies more readily to assist in the cavitation process. It was decided to study a range of alloys to find out whether increasing amounts of an alloying element would cause any progressive increase in, or modification of, the cavitation in copper. Nickel was chosen for this purpose, since it is soluble in copper throughout the whole range of alloys. A further advantage was its low vapor pressure, which enabled the preparation of the alloys in vacuum and the consequent reduction of their hydrogen content. It has been suggested that cavities may be nucleated by the migration of hydrogen atoms to the less regular atomic spacing at the boundary, and their combination to form molecules. The latter being too large to diffuse back into the lattice, form stable cavities into which vacancies could condense. PREPARATION OF ALLOYS All alloys, ranging from pure OFHC copper to 43.7 at. pct of nickel (carbonyl), were prepared in a vacuum furnace employing high-frequency induction heating. When a charge was melted, vigorous gas evolution occurred initially, after which the pressure was reduced to 10-4 mm Hg, using an oil-diffusion pump. After remaining molten for a further 1/2 to 1 hr to aid degassing, the melt was allowed to solidify in the crucible. In this way contamination by gases evolved from the surface of a separate mold was avoided. The list of alloys prepared is shown in Table I. The percentage of hydrogen present in the OFHC copper was reduced from 0.0054 at. pct to 0.0012 at. pct, as measured by a vacuum-fusion method. The alloys were cold-rolled to 0.03-in.-thick strip, and were homogenized in vacuum for 1 hr at 900°C after every 30 pct reduction. At a thickness of 0.05 in., the strip was held at 450°C for 24 hr under high vacuum (10-5 mm Hg) in an attempt to reduce the hydrogen content still further. Tensile specimens were prepared with a gage length of 1 in., and were finally annealed for 2 hr at 800°C to give an average grain diameter of 0.1 mm. TENSILE DEFORMATION The specimens were deformed in a tensile straining machine operated by a synchronous motor at a constant rate, equivalent to 1.7 pct per hr on a 1-in. gage length. The specimen and grips were contained in a vacuum jacket. A pressure of 10-2 mm Hg was maintained, which was sufficient to prevent surface tarnishing of a specimen held at 650°C for 24 hr. Tests were made between 20. and 650°C and the temperature was controlled to within ±3° over the gage length. The load was measured by the deflection of a cantilever spring. a) Mechanical Properties-The ductility curves shown in Fig. 1 fall into two groups. Figs. 1(a) and (b) for copper and the 5 pct nickel alloy, respectively, show a continuous fall in ductility with a steep fall between 200° and 400°C. Figs. l(c) to (f) show the same sudden loss of ductility between 200° and 400°C. With higher temperatures, however, there is a recovery in ductility values to a maxi-

Jan 1, 1959

By D. R. Uhlmann, T. P. Seward, O. Chalmers

A magnetic field has been used to damp out liquid convection during the solidification of castings. Ingots of Al-2 pct Cu were poured from various sperheats (10" to 65°C) into a room-temperature graphite mold located between the poles of an electromagnet. The effect on ingot structure of varying the strength and time of application of the magnetic field was investigated, and the results are interpreted in light 01- current theories of ingot structure. In the solidification of alloy systems, thermal gradients in the melt and differences in density of the constituents are expected to produce convective motion in the liquid. The thermal convection caused by temperature gradients should be present during the freezing of both alloys and pure materials, while the solute convection caused by density differences should be of concern only for alloys. The possible influence of this natural convection on the structure of castings has been discussed by Ruddle,&apos; Chalmers, and Tiller. More recently, an experimental investigation of such effects was carried out by Cole and Bolling. These workers took stationary molds containing lead- and tin-based alloys and. using a brine solution. quenched them from various superheats above their respective liquidus temperatures. When grids were placed across the mold diameter to suppress convection, the grid region was later observed to contain a larger percentage of columnar grains than other parts of the casting or than similar castings poured without the grids present. From thermocouple measurements, they found the temperature in the grid region to be higher than that in the region outside the grids throughout the freezing process, and concluded that convection should be an important mode of heat transfer in normal castings. In addition to such convection arising from thermal gradients or differences in density of the constituents, a further source of convective motion, which we shall call "momentum convection", may be particularly important in small (laboratory-size) castings. By this term we refer to the convective motion produced in the initial pouring process, a motion which is damped out as the linear momentum and angular momentum of the liquid are dissipated. Besides these sources of convection, which are present to some extent in all castings. external influences may also be effective in producing convective motion. Examples of such "forced" convection which have been discussed in the literature include stirring the melt, shaking the mold, rotating the mold, and so forth The purpose of the present study was to examine the effect of convection on the structure of castings poured into a cold mold. In this work, a magnetic field was employed to damp out the convective motions within the liquid, and hence control the extent of con- The effect of a magnetic field on convective currents in a conducting liquid is to induce eddy currents which oppose and damp out the convective motion. vection. The technique of magnetic damping was previously used by Utech and F1emings" in their study of convective effects on impurity banding and other substructure in alloy crystals grown unidirectionally from the melt. In their investigation, fields as small as 200 gauss were found to be effective in damping the convection currents which influence the banding. I) EXPERIMENTAL TECHNIQUE In the present study, alloys of A1-2 wt pct Cu were poured into a room-temperature graphite mold. The mold, in the shape of a circular cylinder, 2 in. ID, 2-3/4 in. OD, 5 in. inside height, and 5-1/2 in. outside

Jan 1, 1967