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By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By C. E. Brown, D. C. Helms, O. W. Shimer

The early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. . The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 3½ million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20" to 90 and some are on the invert in many sharp folds and faults. Planning The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been . maintained. Locations of stripping areas are determined as follows: I. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness

Jan 1, 1944

By W. R. Ingalls

THE present administration has made sincere and effective efforts to reduce the expense of the Federal Government, but it has reached a point beyond which it seems impossible, or anyway extraordi-narily difficult, to go. This is ascribable to the large part of the budget that is represented as war expense. There is no doubt that this spells high taxation for many years to come. Nevertheless, although a large part of the taxation will be attributable to the war, the paying out of the proceeds of that taxation by the government will not be war expense, except in minor part, as will be hereinafter made clear. It will be useful to explain the economic meaning of this situation, for it has bear-ings upon several open questions, such as a bonus to the ex-soldiers, the foreign debt accounts, etc. The expense of the war on the part of the American people was in the main paid concurrently with its prose-cution. This was necessary. Warfare is not conducted with money, but with materials and labor. Except for such previous production as was represented by stocks of goods, the requirements had to be supplied by coincident production. With the end of 1918 our war expense ceased, save for such production, e.g., of ships, that was allowed to run on unchecked, and the indemnities that had to be paid for cancelled contracts. When those matters have been settled we shall be done, barring one important thing. Of course, our war expense began to contract right after the armistice and shrunk rapidly with the demobilization of the troops in 1919. If we had not been able to obtain all needful material from our own sources and had been constrained to borrow it from foreign countries, incurring a foreign debt, we should have been in the quite different posi-tion of having to repay that material, or its equivalent, during subsequent years. The European countries had to come to us for such supplies. This outlines the fundamental difference between their present situations and ours. We were therefore compelled not only to furnish materials and man-power for our own warfare but also much for the Allies.

Jan 3, 1923

By W. C. Knopf, I. M. LeBaron

In the Carlsbad area potash is dry-mined and wet-concentrated. Wet concentration involves recircu-lation of saturated brines, with resultant difficulties of brine disposal and inherent losses in recovery through solution of the KCl. A dry beneficiation process for potash minerals would offer many advantages over present methods. International Minerals & Chemical Corp. has been working on development of a dry process for some time. This article is a progress report. Potash ores available in this country are largely mixtures of halite and sylvite contaminated with slimes and often with many sulfate and magnesium minerals. Electrostatic concentration of KCl when the contaminating minerals are in low percentage has been accomplished. Continuous production of better than 60 pct K2O concentrate from high potassium sulfate ores has not been demonstrated at the present time. Laboratory Procedure: Laboratory work on electrostatic beneficiation of potash minerals has been carried out using both pure crystals and mined ore. Electrostatic separation of the two main components of potash ore, sylvite (KCl) and halite (NaCl), is accomplished by first heat-treating the ore to allow for electric charging of the particles. Preferential exchange of' electrical charges between different mineral particles through surface contact is the principal mechanism involved. After proper conditioning of the particle surfaces, the oppositely charged minerals are dropped vertically into a horizontal electric field having a field gradient from about 5000 to 15,000 v per in. The particles are free-falling in the field. A suitable power supply is used to produce the proper total voltage for the electric field. Total required voltage is, of course, a function of electrode spacing. A typical electrode arrangement with power supply is shown in Fig. 1. In general, the total voltage on any system is 75,000 to 90,000 v. Power consumption is negligible, as leakage at insulators and corona discharge are the main losses in the system. Optimum preheat temperatures for pure material components generally are not the same as for mined minerals. Fig. 2 shows clearly that maximum recovery on a 50 pct pure KCl, 50 pct pure NaCl mixture occurs at a preheat temperature of about 600°F. In this test the preheat mixture was allowed to cool to about 225°F before dropping through the electric field. The optimum temperature for sep- aration is practically never the optimum temperature of preheat. Optimum separation for mined Carlsbad potash ores occurs when a preheat temperature closer to 900°F is used, as shown by Fig. 3, which plots percent sylvite (KCl) in the concentrate and tails as a function of preheat temperatures. Here again the ore was allowed to cool to about 225°F before separation. It should be noted that efficiency of separation increases continuously with increasing preheat temperatures until incipient fusion of the ore takes place at about 950°F. The increase in optimum preheat temperature for Carlsbad ores over the pure minerals can be traced to the effect of the clay slimes intimately associated with the mined potash. If the slimes associated with the ore are removed by washing with alcohol or other non-aqueous material, the necessity of preheating to the high temperature is removed. This temperature range has been proved critical within these limits during continuous pilot plant operation. Concentrate and tailings grade and optimum recovery also are functions of the temperature of the potash mineral particles during separation in the electric field. Fig. 4 presents data indicating that feed to the rougher pass should range between 150°F and 275°F for best results. It has been found by subsequent pilot plant work that these temperatures can be maintained in actual operation.

Jan 1, 1959

By O. P. Dolph

SPANIARDS were probably the first to mine the rich surface ore in the veins cutting the rhyolite capping that outcrops on the hills of La Mazata, oil the Allyones side of the Magdalena valley in Jalisco, Mexico, although the name comes from a word of Indian origin meaning "deer". The camp is about 12 km. west of Magdalena, a town on the Southern Pacific Railroad, and about 17 km. north of Etzatlán, on the Mexican National Railroad, at an elevation of 4500 ft. The climate is subtropical with no extremes of heat or cold, the rainy season beginning in June and ending in October.

Jan 1, 1938

By Frank G. Breyer

C ONDITIONS have not been favorable for new developments in any line. It has been a period, how- ever in which recent developments have been subjected to the severest tests. Those which have been able to hold their own in the severe competition of 1932 must be considered fully proved commercial processes. The continuous vertical-muffle retort plant at Palmer- ton is reported to have been in operation at practically full capacity throughout the year. The high quality of metal produced and the low operating costs are factors which have kept this plant running when many of the older furnaces were shut down. The plant at Meadow- brook, W. Va., is also reported to have been in steady operation throughout the year. Average retort life is said to be better than two years with about three-quarters of the original retorts still in operation after 2 ½ years.

Jan 1, 1933

By J. A. Herrick

FOR a long time, especially in Europe, heavy pieces of forgings, such as cannon, armor plates, marine shafting, etc., have been steadily augmented in size, more particularly since steel has been substituted for wrought iron. To keep pace with these forgings several, very large hammers have been, from time to time, erected. The most powerful and thoroughly appointed of all now in operation is that designed and built by Messrs. Schneider & Co. at their works at Creusot, and it is the design of this communication to give to the members of the Institute a concise description of this remarkable piece of mechanism, which I have taken from an article published in the Annales Industrielles. This hammer is rated nominally at 80-tons power, but its capacity is, in reality, far greater, as will be seen by the comparative figures given later. The complete plant, comprising the hammer, the cranes, the furnaces, and the building which shelters the whole, is distin-

Jan 1, 1880

By H. F. Hebley

In recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and cleaning of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal. Illustrative of this condition is a table of ash contents for the various petrographic constituents of Illinois coal (No. 5 bed) as given by Mitchell' (Table 1).

Jan 1, 1934

By ARTHUR THACHER

PRIMITIVE man supplied his wants as they arose; as he became more civilized he anticipated them by producing more regularly and storing the products for future use. This tended to cheapen' production and prevent ' violent fluctuations and therefore tended to increase consumption. In order to anticipate our wants, we must know what these wants will be, and this can be .determined only by statistics. 'While we have made great progress in gathering statistics, they are still far from what they should be; especially metal statistics. We determine fairly, well the amount produced, but this does not answer all inquiries because of the erratic conditions of mining, it is necessary to carry larger stocks of metals than of most other articles; moreover, as metals are more or less durable, it is difficult to determine the actual consumption. We often count under consumption what is being produced and sold, while the actual consumption is what is being worn out.

Jan 1, 1921

By Edward Keller

(New York meeting, February, 1912.) IN a paper, entitled A Uniform Method for the Assay of Copper Material for Gold and Silver,1 A. R. Ledoux invited the assayers of this country to contribute to a symposium, in which the results of their assays of given samples of copper-matte and metallic copper would be made comparable. This symposium 2 appeared about one year thereafter; and through it and its discussion, first became generally known the fact that the ,gold-yield by the all-fire method of assaying is usually higher than by the so-called combination (wet and dry) method, in which nitric acid is employed as a solvent for the copper. In the publication alluded to, the supposed cause of gold-losses in the latter method was declared to be the solvent action of copper nitrate, or of the reduction-products of the nitric acid, upon the gold. Up to a very recent date, gold has been held to be insoluble in pure nitric acid. (The solvent action of any chlorine present in the nitric acid must here properly be disregarded as belonging in the realm of carelessness. Among later allusions to this topic, W. R. Tan Liew 3 ascribes the solution of the gold in the combination-assay entirely to the action of nitrous acid at the high reaction-temperature of copper and nitric acid ; F. B. Flinn 4 a believes the low result in gold to be due exclusively to mechanical losses-finely-divided gold penetrating through the filter-paper-but presents no experimental data confirmative of this belief; and 0. Pufahl 5 attributes the solubility of the gold in some coppers to the presence of selenium-a view which appears to be shared by many as- 1 Trans., xxiv., 575 (1894). 2 Trans., xxv., 250 (1895). 3 Engineering and Mining Journal, vol. lxix., No. 16, p. 469 (Apr. 21, 1900). 4 Engineering and Mining Journal, vol. lxxxvii., No.11, p. 569 (Mar. 13, 1909). 5 Lunge, Chemische Technische Untersuchungs Methoden, vol. ii., p. 229 (1900).

Jul 1, 1912

By J. K. Kerver, J. S. Osoba, J. G. Richardson, J. A. Hafford

A detailed study of a number of methods of relative permea-abilitv measurement has been made in a search for the tech-niqrle most suited to routine analysis of cores taken from reservoir rock. It has been found from tests run on the same samples of core material by a number of techniques that the Penn State, Hassler, Hafford, and dispersed feed techniques all yield results which are felt to be reliable. Conditions under which the faster single core dynamic technique may be used are described. Further work on the calculation of relative permeabilities to oil from data obtained by the gas drive method is needed before this latter rapid method can be utilized. Correlations between theoretical studies and experimental results have been obtained in studies of the boundary effect. pressure distribution in two-phase flow, and gas expansion effects. Previous conclusions that the effects of the outflow boundary could be made negligibly small have been substantiated. Results of experimentally determined oil and gas pressure distributions along a core sample during flow are presented. Further studies of the effects of rate of flow in the measurement of relative permeability-saturation relations have shown that results are independent of the rate of flow as long as the flow rate is below the point where inertial effects commence. An analysis of the effects of a severalfold expansion of gas along the flow path indicates that while saturation gradients are induced in the test sample, the errors caused by this phenomenon in relative permeability measurements are small. INTRODUCTION Many pages of literature have been devoted to pointing out the need for relative permeability-saturation relations in reservoir engineering. One of the most attractive ways of obtaining this information is by the analysis of samples of core material taken from the formation in question, and again literature has described man); methods for obtaining these data. It is the purpose of this paper to present the work that has been done in the study of some of these published methods together with some other methods that have been recently developed in this laboratory. Also, a study of some of the factors that influence the laburatory determination of relative permeability-saturation relations is presented. FACTORS WHICH AFFECT LABORATORY STUDY OF FLUID FLOW THROUGH RESERVOIR ROCK To determine relative permeability-saturation relations of samples of reservoir rock in the laboratory, it is important to know what factors affect these measurements in order that the magnitude of these effects can be ascertained and steps then can be taken to eliminate or, in some cases, to minimize them. The factors that have been investigated are the boundary effect, the effect of gas expansion. and the rate effect. Boundary Effect In laboratory experiments in which two immiscible fluids are flowed through a porous medium, there exists a discontinuity of capillary properties at the outflow face. This discontinuity exists became the fluids pass from a region of finite capillary pressure in the sample to a region of zero capillary pressure in an open receiving vessel. The capillary forces existing in the core caupe the rock to tend to retain

Jan 1, 1952

By J. J. Kramer, G. W. Wiener, K. Foster

The effects of the primary grain size and sheet thickness on the secondary growth rates of grains with (100) surface planes were studied in 3 pct Si-Fe sheets. This secondary grain growth was carried out under conditions in which the {100} plane had the lowest surface free energy. The value of the surface energy difference, between the (100) plane and the random matrix planes was found to he only about 3 pct of the grain boundary energy, indicating that most of the driving force for secondary growth is supplzed by grain boundary energy. A method for obtaining cube texture in 3 pct Si-Fe sheets by a secondary recrystallization process has been reported.' It has been demonstrated that a difference in surface free energy between the (100) plane and other planes is responsible for this growth, where the (100) plane has the lowest surface energy. A semiquantitative relation has been derived for secondary grain growth in sheets where primary grain growth has proceeded until the grains have grown through the sheet and the average grain diameter in the plane of the sheet is from one to two times the sheet thickness. Then, the linear growth rate, G, for the secondary grains can be given by where M is the grain boundary mobility, is the grain boundary free energy, is the average primary grain radius, A is the average difference in surface free energy between the (100) plane and planes of other orientations, t is the sheet thickness, and C is a term first proposed by zener6 which acts as a negative driving force, the effect of inclusions in holding up grain boundary motion. Since the problem of grain growth being discussed is under conditions where the matrix grain size is at least equal to the sheet thickness, the radius r is, of course, a function of the sheet thickness. The term B/r is the grain boundary driving force normally associated with inclusion inhibited or texture inhibited secondary recrystallization. Here, however, the term is modified to account for the fact that growth occurs in thin sheets. The term is the additional driving force available because of the difference in surface free energy. The purpose of the present work has been to evaluate the driving force terms of the growth equation by studying growth rates of (100) secondary grains as a function of sheet thickness and primary grain size. From these data it has been possible to determine the relative values of grain boundary energy, surface energy difference, and the inclusion term, C. EXPERIMENTAL PROCEDURE A 3 pct Si-Fe alloy was melted and cast under a helium atmosphere using electrolytic iron and a pure commercial grade of silicon as raw materials. The alloy was hot and cold rolled to a thickness of 0.6 mm, and samples approximately 5 in. long by 1 1/4 in. wide were cut from the cold-rolled sheets. Four different primary grain sizes were obtained

Jan 1, 1963

By H. Y. Jennings

An extensive field and laboratory experimental program was carried out to compare the waterflood behavior of carefully preserved soft and unconsolidated cores with measurements on the same cores after extraction. Results obtained from using idealized consolidated and unconsolidated porous media in which wettability could be carefully controlled were contrasted with the preserved core data. The controlled tests on idealized porous media investigated the effect of wettability, flood rate, core length, core permeability and consolidation on the displacement of high viscosity oils. It was concluded from these studies that waterfloods are more favorable when carried out with crude oil in preserved soft and unconsolidated cores than with the same cores after they have been extracted and re-saturated. Waterfloods are usually more favorable when carried out with crude oil in extracted .soft and unconsolidated cores than with refined oil of the .same viscosity in the same cores. The less favorable behavior of extracted soft and unconsolidated cores compared to preserved cores is due to alteration of the core by extraction. Preserved cores saturated with native water and oil should be used for laboratory displacement experiments because they more accurately reflect true reservoir behavior INTRODUCTION The demand for low gravity crude oil created by refinery modernization has focused attention on increasing the production of this viscous crude oil. Billions of barrels are in place in fields that are depleted, or nearly depleted, by primary production mechanisms. Since low gravity reservoirs are relatively recent, geologically, the solid matrix material is usually soft and unconsolidated sand. Such formations are also characterized by a high clay content. Evaluation of sophisticated oil recovery processes with the associated high capital investments has increased the demand for special core analysis tests on material from these soft and unconsolidated sand reservoirs. Data in this paper have resulted from an extensive field and laboratory experimental program. The initial objective vras to provide soft and unconsolidated sand cores for laboratory measurements with as little alteration as possible from their reservoir condition. A secondary objective was to compare the waterflood behavior of these carefully preserved cores with measurements on the same cores after they had been extracted and resaturated. When the comparison showed markedly different behavior the final objective was to attempt to explain the difference by making measurements on idealized porous media free of clay in which initial wettability could be carefully controlled. EXPERIMENTS MATERIALS Core Material The preserved cores used in this study were obtained with as little alteration as possible from their reservoir conditions. Special techniques were developed to satisfy this objective. The cores were cut with native crude whenever the crude had the necessary properties to satisfy the minimum drilling fluid requirements. A pure hydrocarbon chromatographic tracer was added to the crude to provide a simple, safe and inexpensive method to distinguish between oil filtrate and formation oil. Details of the tracer technique used in this study and the procedures used to handle and process the soft, unconsolidated cores have been published.' The core samples were then preserved and packaged at the well site with a dip-applied strippable plastic, or by using a rubber sleeve from a rubber-sleeve core barrel. The final step was to insure that the carefully taken and preserved samples were not altered by processing in the laboratory. Some soft and poorly consolidated sands were carefully shaped in the lab and encased in a protective mounting without disturbing their three-dimensional integrity. Many samples were so poorly consolidated that they literally flowed from the package when the seal was broken. A technique was developed to obtain cylindrical plugs from these samples by using liquid nitrogen as the drilling fluid in a conventional core-drill, drill-press assembly. The idealized porous media consisted of sintered rods of Alundum RA 139, outcrop sandstone identified as Al-hambra sandstone and packs of No. 130 Nevada sand. This sand is 95 per cent 140-200 mesh. (Physical properties of these porous media with those representative of preserved cores are in Table 1.) The natural cores and most of the idealized porous media were 1 1/2-in. in diameter and 3-in. long. The samples used to study the effect of core length were 1 1/2-in. in diameter and 12-in. long. Liquids Water and oil produced from the formations being studied were protected from the atmosphere and collected in carefully cleaned glass or plastic-lined containers. The production was free of chemical additives such as emulsion breakers and corrosion inhibitors. The crude oil was

Jan 1, 1967

By G. V. Raymor, James T. Waber, I. Rex Harris

The lattice parameters of a series of fcc alloys of cerium and thorium were measured at 93 " and 298OK. Lattice parameters were also estimated for 171OK. Substantial deviations, y, from Vegard's law were observed. Although y was negative at the two higher temperatures, it was positive and large at the lowest temperature. A variety of models, which have been proposed in the past, were considered, and the calculated values of y were compared with the observed values. The best agreement was achieved with values computed with Friedel's equation. THE purpose of this investigation was to determine the effect of temperature on the lattice parameter and on deviations from Vegard's law of Ce-Th alloys. A large negative deviation from Vegard's law was first observed independently by Weiner, Freeth, and Raynor' and Van vucht2 in the room-temperature lattice parameters of Ce-Th alloys that form a continuous series of solid solutions. This observation was confirmed by Evans and Raynor. The allotropy of unalloyed cerium was reviewed recently by Gschneidner, Elliott, and McDonald. In two subsequent papers,5" these authors reported the influence of various alloying additions on the y= transformation, which occurs below room temperature. Although other rare earths tend to stabilize the double-hexagonal phase, thorium, plutonium, and scandium as solutes tend to stabilize the normal fcc phase. With addition of sufficient thorium as a solute, there is evidence that the formation of is suppressed and it becomes possible to pass continuously with decreasing temperature from the room-temperature phase to the fcc a phase. Thus there is a closed loop which is similar in many ways to the y loop well-known in ferrous alloys. A closed field also occurs in the pressure-temperature "equilibrium" diagram of unalloyed cerium. Because of interest in the effect of thorium additions and their influence on the a and phases, lattice-parameter measurements were made at low temperatures on the fcc phase for a series of alloys ranging from 10 to 90 at. pct Th. The results obtained at three temperatures are shown in Fig. 1. Evans and Raynors analyzed the deviations from Vegard's law in Ce-Th alloys in terms of changes in the occupancy of the 4f electron level in cerium,

Jan 1, 1964

By F. R. Brotzen, J. Taranto

SEVERAL investigators have computed stacking-fault concentrations from X-ray diffraction data.'-' The method generally employed relates the line shift to the stacking-fault probability. In this investigation platinum filings of 99.99 pct purity screened to -325 mesh were studied after having been subjected to various annealing treatments. The lines were measured on a General Electric XRD-5 spectrogoniometer using CuK, radiation. The centroid of the broad reflections was determined by the method proposed by pike.' The stacking-fault probability was calculated by the formula given by Warren and warekois,3 with the assumption that all stacking faults were on the (111). Various high-angle reflections were used, but most data collected refer to the shift in the (400) reflections. When the filed platinum powder was annealed at 1200°C for 20 min the stacking fault concentration was too small to be detected. The stacking-fault probability in freshly filed specimens, as determined by the line shift relative to the annealed specimen, was about 0.016, Fig. 1. If the faults would be created only by extended dislocations, the dislocation density in the filed specimen would be about 3X1012 cm-2. The average stacking-fault width of about 21 which was used in this computation, is that given by Thornton and Hirsch.7 The mechanism by which stacking faults are annihilated during annealing is not yet fully understood. The isothermal results obtained do not seem to support the simple hypothesis of a first-order decay. On the other hand, the analysis by Kuhlmann, Masing, and Raffelsieper8 for the loss of dislocations during recovery agrees much better with the experimental data of this investigation. This analysis yields an activation energy of 29 ± 8 kcal per mol for the disappearance of stacking faults in cold-worked platinum during annealing. Even if one takes into account the lack of accuracy inherent in this X-ray method, the activation energy found is substantially less than that of self-diffusion in platinum, i.e., 61.6 kcal per mol.9 The results therefore suggest that processes other than dislocation climb, which involves the activation energy of self-diffusion, are responsible for the loss of stacking faults in platinum during annealing. The broad reflection lines became sharper early in the recovery process, Fig. 1. The sharpening occurred well before the stage during which stacking faults disappear. This lends support to Nowick's10

Jan 1, 1962

By E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By Henry D. Hibbard

FoR the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seem to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machincry, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume. Into which class an ingot will fall depends on the gases of the steel,

Jan 1, 1920

By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By William Romanoff

IN AN ARTICLE on "Recovering Smelter Dust and Oxide," published in the Engineering and Mining Journal (Vol. 131, No. 2), the authors briefly described some dust-recovery equipment and its operation at a secondary-metals brass-smelting and refining plant. A description of our experience in overcoming certain operating difficulties may prove of interest or value to those who are confronted with some of the same problems or who should equip their furnaces with dust-collecting equipment. The dust loss from reverberatory smelting and refining of brass con¬sists largely of zinc, with smaller percentages of lead, tin, and copper in the order named. At the Kramer plant, the fume discharge from the two stacks amounted to 3 to 4 tons of solids per day, making a dense smoke. With dust equipment in operation, the discharge from the stacks is invisible and approximately 2500 lb. of zinc and other metals is recovered daily thereby from each furnace operating.

Jan 1, 1933