Search Documents

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3', as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By C. K. Leith

CERTAIN ideas on iron and steel sanctions to follow originated in a series of conferences held under the joint auspices of the War Department and Brookings Institute in Washington last spring. The views presented may be regarded as those of substantial segments of the steel industry. In view of the fact that steelmaking capacity can be so quickly converted to the production of armament, any effective control must necessarily include the entire steel industry and not solely the parts devoted to the production of implements of war. It must also be exercised all the way from production and shipment of raw materials through their ultimate conversion into finished products and use. Control will be dis- cussed under two main headings: (I) control of raw materials at the source; (2) control of steel capacity within the Axis countries.

Jan 1, 1944

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

WALTER E. GASP, Vanadium, Colo. (communication to the Secretary*).-Having enjoyed associations with the authors of this paper while on the Anaconda geological staff, I want to express my appreciation of it as a contribution to economic geology very direct in its application to ore deposits. The conclusions reached seem to me to show that concrete generalizations can not be made over very wide areas as to structural relations of ore deposits, but taking each district separately data of great value has been presented. Looking over thin sections of Montana rocks, among these a collection belonging to Mr. Billingsley and some prepared by myself, one important point in the Butte area has come to my attention which I would like to discuss. Related to the batholithic intrusion, there are a number of various types of both the earlier andesites and the later rhyolites, especially of the rhyolite. Some of this rhyolite is composed- so predominantly of plagioclase and quartz as to be more properly called dacite, and near the volcanic centers the different phases are even more numerous, the quartz in some becoming a very minor constituent and confined to the ground-mass. Some portions of these rhyolitic extrusives assume ,deep reds and grays, and in the hand specimen may very easily be mistaken for andesite of the older period that has been altered by weathering or by baking near the intrusive granite contact; but thin sections of such specimens remove this color effect and present so clearly all the minute details of texture and mineral composition that they are in every respect identical and indistinguishable from the commoner types of the rhyolite. The andesites generally are augitic rocks with smaller plagioclase feldspars than the rhyolites and exhibiting a different arrangement. Therefore the so-called red and Clark gray andesite near Butte is not a portion of the pre-batholithic rocks, but a. phase of the rhyolite, and the authors, in assuming that "roof pendants or large inclusions of andesite are found

Jan 10, 1917

Discussion of the paper of WALTHER MATHESIUS, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 539 to 555. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-This paper answers. partly the difficult questions which have come up as to why it is not economical to use higher blast temperatures in the smelting of Mesaba ores, such as the high temperatures used in European practices, and the answer is very plain that the ores will not stand the higher temperature. But the paper does not go into detail as to what special difficulties were found with the higher temperature of blast, and I would ask the author to kindly specify them. W. A. FORBES, New York, N. Y.-A large part of the troubles that furnace men experienced in using high-blast heats in smelting Mesaba ores in the early days of using Mesaba ores, was clue to the attempt to use these soft ores on furnaces having the same lines as the furnaces used in smelting the hard Old Range ores. As the result of observation and study, the dimensions of the lower part of the blast furnaces have been changed and the difficulties of the blast-furnace men in operating with a large percentage of Mesaba ore and high-blast temperatures have been largely overcome. The changes I refer to in particular are: (1) steepening the angle of the bosh; (2), decreasing the height of the bosh; (3) increasing the diameter of the hearth. JOSEPH W. RICHARDS.-Mr. Forbes's answer is quite satisfactory, and the moral which it points is that when the furnace is run with a higher temperature in the smelting zone, the furnace lines which were adapted for the lower temperatures are not necessarily those best suited for the higher hearth temperatures. If. enriched blast were used in a furnace, and higher temperatures run, it would be found necessary to further modify the lines of the furnace to meet the new conditions and to get the maximum output with economy. J. E. JOHNSON, JR., New York, N. Y.-It seems to me this is one of the few papers which could well have been a little longer. The data which Mr. Mathesius has given us, I think should be considered in connection with the paper which Mr. Brassert read before the American Iron and Steel Institute last spring, in which he described how they had obtained remarkable results with furnaces with steep but very short boshes; the angles have been raised to 80°, and the boshes made so short that they no longer appear as a conspicuous part of the shape of the furnace.

Jan 5, 1915

By E. F. Sturcken, J. W. Croach

A grain orientation distribution function, P(u,F), was developed for use in predicting physical properties in oriented metals. Examples are given of the use of the function to predict thermal expansion coefficients in rolled uranium rods and plate. The P(u,F) function was synthesized from X-ray difpaction intensity measurements, Ii, norrnally used to plot inverse pole figures. The symbols u and F specify the angles that the crystallographic axes of the grain make with the normal to the sample surface and P(u, F) gives the number of grains oriented in each direction, (u,F). P(u,F) is obtained from a least squares fit of the Ii to an orthonormal set of spherical harmonic functions. The P(u, F) function was also used to define a quantity, J, which is a measure of the departure of the orientation distribution from unifomzity (or "randomness"). The J parameter may be used to follow, quantitatively, the amount of preferred orientation induced as a function of mechanical working or heat treatment. An example is given of the application of the J parameter to prefevred orientation studies of hot- and cold-rolled uranium rods and hot-rolled uranium plate. Because P(u,F) is derived from relative intensity measurements by the powder diffraction technique, it is applicable to material with large absorption coefficients and/or grain size and is particularly suitable for characterizing the preferred orientation of large numbers of samples such as fuel elenzents for a nuclear reactor. IN general the physical properties of an oriented metal depend on the direction in which the properties are measured. Hence to predict physical properties the grain orientation must be known as a function of the direction of the specimen. The conventional methods of expressing preferred orientation measurements are the pole figure1 and the inverse pole figure.2-8 Both methods are difficult to use for predicting physical propertiess because they are graphical and because they are stereographic projections and hence are not "area-true." In the present report a quantitative orientation distribution function, P(u,F), is synthesized from pole density measurements normally used to plot inverse pole figures. For inverse pole figure plots the pole densities, pi, are obtained by powder dif-fractometer intensity measurements of their reflections from a flat surface of the sample, normal to the direction of interest. Each pole density, pi, represents a single orientation, i, and is proportional to the volume of material with orientation, i; hence a set of pi gives an approximation for the general orientation for the sample direction measured. The expression8'7 for calculating the pole densities, pi, from the diffraction measurements was previously

Jan 1, 1963

By J. S. Osoba, J. G. Richardson, F. M. Perkins

Laboratory experiments have shown profound diffcrences in the behavior of so-called "fresh cores" from the East Texes field and of the same cores after ex~ractio~l with organic solvents. The residual oil satura/ion remaining after waterflooding fresh cores was appreciably lower than the corresponding saturations after flooding extracted cores. This behavior was also reflected in the water-oil relative permeability-saturatiorl relations, which were more favorable for high oil recovery from the fresh cores. These differences were evident not only in the amount of residual oil left after wafer flooding, but also in the saturation water remaining in the core after displacernent by oil. Residual water saturation after displacernetzt of water by oil was higher in the fresh cores than in the extracved core,. Capillary pressure-saturation relations were also different for the fresh crnd extracted cores. Imbibition experiments indicated that both fresh and extracted Bast Texas cores imbibed water spontarteOLISIY, but- the rate of imbibition of water was higher for samp1es after. extraction than it was for fresh core. material. INTRODUCTION Several years ago a series of waterflooding tests was made in the laboratory on a number of Woodbine core samples from the East Texas field. These samples had been stored in containers open to the air and were extracted with organic solvents before they were subjected to the laboratory tests. After water flooding, the residual saturation of kerosene, which was the oil used in the tests, was found to average about 30 per cent. This saturation was higher than expected. In investigating the circumstances which might have been responsible for such a high residual oil saturation, attention was given to possible changes in wetting properties of the rock brought about by the procedure employed in extracting the cores. Preliminary results indicated that the explanation for the high residual oil saturation lay in the wetting behavior of the cores, though what effect extraction had on this behavior was not clear. In consequence, the work described in this report was undertaken in an attempt to investigate the mechanism responsible, and to ascertain the actual residual oil saturation to be expected in the reservoir after water flooding. It was soon found that there were profound differcnces in the behavior of so-called "fresh cores" from the East Texas field and of the same cores after extraction with organic solvents. These differences were evident not only in the amount of residual oil left after water flooding, but also in the saturation of watet remaining in the core after displacement by oil. The complete explanation of this behavior is not yet apparent. The description of work and results described in following sections, therefore, must be considered as an interim report presenting facts which must await additional information before they can be fully interpreted.

Jan 1, 1956

By Wilford S. Wright

FOR the past four years the management of the Black Hawk Consolidated Mines plant at Mogollon has conscientiously kept accurate records pertaining to cost of operation and the performance of certain equipment. These records have been valuable in coordinating the work in the mine, mill and power plant. Also, as to quantity and kind of equipment and supplies most suitable from the standpoint of economy and dependable operation, they have served as a guide. Through comparison with records at other mines, where the same things are being done in a different way, they have pointed out mistakes to be avoided. No outstanding accomplishments, either in costs or performances, are revealed; in fact, some of the results are perhaps quite inferior to those obtained at similar plants, but it is with the thought that more records should be published for the benefit of the mining profession that the author presents these data. To other operators and to mining engineers who are called upon to make estimates for prospective operations, the information herein should be helpful. GENERAL CONDITIONS Mogollon is in the southern part of Catron County, southwestern New Mexico. It lies near the western border of the Mogollon Range, 14 miles east of the Arizona line. Silver City, 80 miles to the southeast, is the nearest railroad point. The connecting road, over which supplies are hauled into camp by trucks, is an improved highway for about 50 miles; the remainder consists of graveled roads and unimproved steep mountain grades. One general supply truck and one tank truck make daily round trips. Hauling of supplies to the mine has cost at the rate of $0.08 per ton-mile; or, on the basis of ore production, $0.30 per ton mined. Lumber, hauled in from local mills, has cost an average of $30.00 per 1000 board feet, $8.50 of which has been for hauling. The annual consumption averages 108,000 board feet. Lime, hauled from a plant in Arizona, is about the only other item not brought out from Silver City. Fuel oil for the generation of power is the item of greatest hauling expense, the f.o.b. Mogollon cost of approximately $0.06 per gal. being nearly twice the f.o.b. refinery price. Water for power plant, mill and camp use flows to camp storage tanks through a 4-in. pipe line from a spring and intake 3 miles up Silver Creek Canyon. A few times, particularly in the month of June, mill operations have been suspended for two or three days because of water shortage. MINING CONDITIONS During the years 1938, 1939, 1940 and 1941, the mine produced 230,059 dry tons

Jan 1, 1943

Henry Louis, Newcastle-upon-Tyne, England (communica, tion to the Secretary): I have been much interested in Mr. Schmitz's description of the copper-ore bed in the Permian formation of Texas. He compares it with the Mansfeld Kupferschiefer; but it seems to me to present closer analogies with a small deposit on the same side of the Atlantic, in Nova Scotia, which I examined in 1877. I quote entirely from my fieldnotes, made then, and from specimens still in my possession. These copper-deposits are known in several places; but I examined them at the village of New Annan, on the banks of the French river. This district has been determined by Sir J. W. Dawson as being of Permian age, and this determination seems to have been confirmed as recently as 1891 by the operations of the Canadian Geological Survey. The following is the section, very imperfectly exposed in a few shallow levels, described in ascending order: Red sandstone, moderately fissile and markedly false-bedded. Lower nodule-bed, 1 inch to 6 inches thick, of fissile mica, ceous sandstone, containing obscure plant-remains converted into anthracite, chalcopyrite, chalcocite and iron pyrites. Very coarse grit or, in places, red sandstone; thickness and character variable. Upper nodule-bed, 6 inches to 2 feet thick exceptionally, generally about 10 inches. Soft, gray, friable shaly sandstone, with nodules of copper-ore. Red sandstone. All these strata lie flat, in places quite horizontal, in places dipping towards the river at 5° to 10°.

Jan 1, 1897

By Charles White Merrill

Mankind's progress is measured in minerals. Man's emergence from prehistory is marked by passage through a Stone Age and a Bronze Age and into the present era, sometimes called the Iron Age or the Age of Metals. With the evolution of civilization and the development of a modem industrial economy, minerals become more and more important. Structures, roads, and machines are built largely of minerals; the energy to heat the structures and to drive the machines is mostly mineral; agricultural fertility is maintained by mineral fertilizers and water; and military strength is provided by fortresses, armaments, and munitions, largely of mineral origin. Thus in the material world, in the productivity of the economy, access to minerals has paramount importance. Every evidence indicates increasing dependence on minerals in the modem economy, particularly on the mineral fuels as energy sources to provide the power base for advancing industrialization. Both the total and the per capita consumption of almost every mineral is increasing in the industrialized nations. Moreover, nations with predominantly agrarian economies call themselves underdeveloped and universally strive to industrialize. Most mineral consumption trends in the more advanced economies have been greatly exceeding population growth-which itself has been advancing at an accelerating rate-and sometimes have surpassed the growth in real income. Some minerals have only recently been adopted or grown to importance in use. Titanium metal did not appear as a commercial product until 1948, and even coal seriously displaced wood as a source of heat less than two centuries ago. On the other hand, minerals have always played an important role in construction. The prehistoric megaliths that form the dolmens of Salisbury Plain are stone; the pyramids are andesite faced with limestone; and many other ancient structures are built of mineral materials. In modem times the whole course of architecture has been redirected by new building materials, mostly mineral. Most conspicuous is the sky-

Jan 1, 1964

By E. R. Parker, E. A. Smith

Metallurgists and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applica-tions and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. Experimental Procedure Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were

Jan 1, 1944

By E. A. Smith, E. R. Parker

Metallurgists and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applica-tions and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. Experimental Procedure Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were

Jan 1, 1944

BENEFICIATION AND CONCEN'TRATION; FROTH FLOTATION U.S. 4,069,144 - In the froth flotation beneficiation of phosphate rock using at least an acid flotation step and an amine flotation step, the crude ore is dried either during transport or storage or by air circulation immediately prior to classification, and the dried ore mixed with water and classified prior to flotation The preliminary drying substantially eliminates the usual problems with clay slimes G. C. Johnson and A. E. Schweizer, assigned to Mobil Oil Corp. Jan 17. 1978. 4 pp (209- 11) . Filed 1 1-19-75 (633,535).

Jan 1, 1979

By J. E. Harris, J. A. Whiteman, A. G. Quarrell

The graphitizing reaction has been studied in a number of Fe-C-Si alloys in the temperature range 550° to 725°C. The TTT relationships exhibit "C" curve behavior except where nuclei, either foreign or graphite itself, are present before the start of the reaction. It is suggested that the rate -controlling process is diffusion of carbon through ferrite. For the reaction to proceed at the observed rate it is calculated that the matrix surrounding the particles must deform plastically; experimental evidence for this deformation is presented. It is well-established that the decomposition of austenite to pear lite occurs at a maximum rate at an intermediate temperature.l-5 This "C curve" be- havior, which has been reported in a number of other systems,5-10 is a consequence of the relatively low rate of nucleation of the pearlite at small degrees of undercooling of the austenite. The cemen-tite phase in the pearlite is, in turn, metastable with respect to graphite and if steels are held for prolonged periods at elevated temperatures decomposition of the pearlite occurs. It is difficult to predict the shape of the subcriti-cal graphitization TTT (time, temperature, transformation) diagram for, in this case, undercooling does not occur. However, the free-energy change for the reaction does decrease with increasing temperature" (Fig. 1) and it is thus anticipated that the rate of nucleation will fall as the temperature approaches that of the eutectoid. In addition, a decreasing growth rate with increasing temperature is predicted in some circumstances with pure Fe-C alloys. However, apparently similar conditions exist for first-stage graphitization in the austenite range (malleabilization) but no evidence for C curve behavior has been presented in the extensive liter-

Jan 1, 1965

By Milton R. Pickus, Earl R. Parker

THE modern theories of creep¹-4 in general have been based upon the concept of generation and migration of dislocations, with the generation process normally assumed to be rate controlling. The theories are generally deficient in that they fail to take into account many factors that are known to influence creep. The influence of the state of the surface of the test specimen has been almost completely overlooked; yet the present report shows that the nature of the surface may, in certain cases, govern the creep characteristics of a specimen. In the period since Taylor" applied the concept of dislocations to a study of metals, a school of thought has developed that closely relates the plastic deformation of metals to the generation and migration of dislocations through the crystal lattice. It might be expected that the thermal energy required for the generation of a dislocation would be different from that for migration of the dislocation through the lattice. Furthermore, the activation energy for generation would be expected to vary for different parts of the solid metal. It has been predicted that dislocations would be generated most easily at external surfaces, but could also be activated at certain internal surfaces such as grain or phase boundaries. Within the body of the metal a range of values for the activation energy might be expected because of different degrees of disorder at such regions as grain boundaries, impurities, and second-phase particles. The particular value of the activation energy that was rate determining could then depend on the specific conditions of a test. If, for example, the surface atoms were by some means constrained, the generation of dislocations in the body of the metal might become the important factor. On the other hand, other conditions may favor generation at the surface. It is possible then that the creep behavior may not be completely determined by the inherent properties of the metal. Even the environment in which a test is carried out could have a significant effect. In fact it is conceivable that in order to obtain the maximum creep resistance from a given alloy, the surface atoms must be so constrained that the activation energy for generating dislocations on the surface is at least equal to that required for generation in the body of the metal. On the basis of such considerations, and in view of the limited number of publications discussing this subject, it seemed that an investigation of the influence of the state of the surface on creep might yield information of both theoretical and engineering interest. Experiments on single crystals, demonstrating a variation in the mechanical properties due to alterations in the surface layer, have been reported by several investigators.6-13 he results of these experiments have been briefly summarized;14 consequently, the earlier work will not be reviewed here. As an example of these findings the observations of Cottrell and Gibbons may be cited. They reported the critical shear stress of a lightly oxidized cadmium single crystal is greater by a factor of 2½ than a specimen with a clean surface. Materials and Methods Single crystals M in. in diam and 8 in. long were prepared from Horse Head Special zinc, melted under an atmosphere of helium in a large pyrex test tube, and drawn up into a long ½ in. diam pyrex tube by means of a vacuum pump. The cast zinc rods thus produced were cut into convenient lengths and sealed in evacuated pyrex tubes. Single crystals were grown by gradual solidification of the remelted rods. Cleaving the ends of the single crystal specimens chilled by liquid nitrogen proved a simple method for determining orientations from the exposed basal plane from the markings left on the cleaved surface that gave the slip directions with sufficient accuracy for the experimental work. The specimens chosen for the experiments were those having the angle between the basal plane and the specimen axis within the range of 15" to 65". Since zinc single crystals are quite delicate, it was necessary to devise an appropriate method of gripping the specimens in order to suspend them in the furnace and apply the load. Stainless steel collars were prepared having an inside taper, the smaller end of the taper being of such a size that the specimen could just pass through freely. The tapered hole did not extend the full length of the collar; a sufficient thickness of metal remained so that a hook could be attached to provide a means of applying the load and suspending the specimen. One of the collars was slipped over the upper end of a specimen which was supported vertically in a steel jig. The collar was then heated electrically until the end of the crystal melted and filled the collar with molten zinc. At this point the application of heat was discontinued, whereupon the molten zinc quickly solidified, due to the chilling effect of the jig. The specimen was then inverted and the second collar applied in a similar manner. The jig served several purposes: limiting the length of specimen that was melted, providing excellent alignment of the collars with respect to the specimen axis, and protecting the specimen from mechanical damage. Once the specimen was suspended in the furnace and loaded, it was desired to accomplish the surface treatment with a minimum of disturbance of the specimen. Around the specimen was a long pyrex tube, the upper portion of which was approximately 1 in. in diam, and in it was a copper coil of such a diameter to fit snugly against the tube. A specimen, approximately ½ in. in diam and 4 in. long, was suspended by means of a stainless steel rod so that it hung within the copper coil. The lower portion of the glass tube was approximately ¼ in. in diarn, and passing through it was a 5/32 in. diam stainless steel rod which hung from the lower specimen collar. This portion of the glass tube and the stainless steel rod extended through the bottom of the furnace. A T-connector, with suitable packing, was attached to the lower end of the stainless rod to provide a water-

Jan 1, 1952

By B. H. Sage

ATTEMPTS have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-tures1-5 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.? and the temperatures are in the neighbor-hood of 250°F. was investigated.

Jan 1, 1940

By William C. Marshall, Frank G. Norris

THE term "total operation" is meant to include problems that cannot be answered from the standpoint of either the blast furnace or the open hearth separately but must be studied by considering the interrelations of these two processes. There are other ways of expressing this idea, such as reference to the blast furnace and the open hearth as an integrated process or by emphasizing the interrelation and interaction of the two processes. Much progress has been made in metallurgy and other fields by breaking complicated processes and reactions into simpler parts and studying each of these intensively. This intensive study frequently is done under the controlled conditions of the laboratory experiment. The entire process is understood better by this specialized study of each of its parts. This procedure is so satisfactory that an understanding of unit operations is a fundamental requirement of chemical engineering. Much discussion of the open-hearth process is in terms of one heat or one furnace. By this is meant that the conclusions apply to one furnace, wherever it may be. Furnaces seldom occur singly; they are located in groups and these groups are located in steel plants having characteristic blast-furnace equipment. Problems that are affected by the number of furnaces operating, by the number of blast furnaces in the plant and by the fact that the open hearth shop is dependent on the blast-furnace capacity rather than on its own needs for the amount of iron available are among those which, in contrast to "unit operations," we have chosen to call "total operations," Many of these problems, such as charging delays and the general mechanical problem of material handling, are so familiar that merely to define "total operations" brings them to mind. These problems are of such importance that already they have received careful thought and study and probably will merit further study. As will be shown later, these mechanical problems are so intimately related to metallurgical problems of total operations that the effect of certain changes cannot be ascribed with certainty to either a mechanical or a metallurgical cause entirely. Although the problems coming under the general term of "railroading" are included in the problems of total operations, two others are selected for the discussion of this paper. One of these is strictly a problem of composition; the other is strictly a problem of tonnage production. The problem of phosphorus is present whenever basic open-hearth slag is used in the blast-furnace burden. This practice has not secured universal acceptance chiefly because of difference in preference for high-manganese or low-manganese pig iron. If high-manganese (2.00 per cent) iron is to be made, open-hearth slag as a source of manganese is usually cheaper than man

Jan 1, 1943

By Carl Lemke

SOME of the principal metallurgical difficulties en-countered in the differential flotation of lead-zinc-iron sulfide ores arise from the following causes: The oxidized, or partly-oxidized, condition of one or more of the minerals ; impurities in the minerals them-selves; composition and character of the gangue miner-als; soluble salts in the ore; and unfavorable metal ratios. In many of the ores received at a custom mill there are present appreciable amounts of oxidized' or partly-oxidized minerals, although the ores may be substantially sulfides. Often the ores are not oxidized at all when received but on account of operating condi-tions at the mill it is necessary to stock them for several months before they can be milled, and considerable oxi-dation takes place while they are lying in stock. In most ores received at Midvale, when oxidation is pres-ent, the lead and iron sulfides have been more affected than the zinc sulfide, but with some ores the zinc mineral has also become partly oxidized. Some ores, such as those taken from old mine-dumps or from old stopes, may show very little total oxidation, but the greater part of the valuable minerals has been sufficiently acted upon by oxidation to make the minerals very difficult to float. Ores of this character are among the most difficult the flotation operator has to contend with, be-cause the galena, sphalerite, and pyrite are all sluggish in their behavior in the flotation cells. Only a part of the lead mineral will float in the lead circuit. The re-mainder will lag badly and tend to come up with the zinc or, if badly oxidized, will go -through all the flota-tion circuits into the tailing. The zinc mineral, if it has also been affected by oxidation, will act in a man-ner similar to the lead mineral. A hard pull will be required to float a reasonable percentage of it, and this is likely to bring up so much pyrite that it will be difficult to make a zinc concentrate of commercial grade. If it happens that the zinc mineral has not been no-ticeably affected by oxidation it will tend to float in the lead circuit because a hard pull is also required in that circuit in order to bring up the sluggish galena. When only a fraction of the sulfide minerals has become partly altered, or completely oxidized mineral is present in relatively small quantity, it is usually possible to make reasonably clean concentrates of all three sulfides, that is, lead, zinc and iron concentrates. Most of the oxi-dized and semi-oxidized minerals will go into the tailing and the losses will be proportional to the oxidation.

Jan 4, 1927

By E. H. Rose

THE question is often pondered whether the flotation process is still an art or has become a science. The fact is that flotation is a science in so many variables that only art can blend them. It is demonstrable that no less than one hundred variables are involved in any flotation operation, most of them immeasurable on a routine basis. The behavior of every one of them is always governed by orderly and unchanging law, as no man can doubt. There is nothing truly indefinite about that behavior; the only indefiniteness is in our knowledge of it, either in general or from hour to hour in the circuit. In dealing with a simultaneous equation in, say, one hundred variables, all not only affecting the outcome to some degree but many influencing each other as well, it is small wonder that the mineral-dressing profession presents a case history of debate and controversial opinion. The statement of the subject of this symposium-a symposium on flotation machines-seems to delimit and define the matters to be considered and at least the general nature of the conclusions sought. Nevertheless, in such a meeting it is not possible to meditate upon all the variables that do in one way or another affect performance of flotation machines. To attempt it would be much like trying to operate a hundred-ring circus. Perverse variables being what they are, one could expect the elephant in ring 36 to squirt a trunkful of water at the tightrope performer in ring 37 to ruin that artist's act, just as our learning to depress pyrite in the early 1920's ruined the act of the formerly faithful old Callows. HONEST DISAGREEMENTS Selective flotation dates from 1922 or 1923, when several plants established their regular flotation operations on a selective basis. Since then, two decades of efforr have gone into the development of better and better flotation machines. Many have come and gone. The competition has simmered down to perhaps a dozen machines, each one of which is staunchly defended by some operators as being the best for their particular jobs, and as scornfully dismissed by at least a few others elsewhere as being positively the poorest for theirs. These disagreements are honest disagreements, honestly arrived at after plenty of sweat. In many a flotation plant, one machine has been tried out against another under conditions as fair as they could possibly be made. Sometimes the results are on a par but more often one machine shows a consistent and unmistakable margin of superiority over the other. In equally honest and enlightened tests, machine A may win over machine B in one place, and machine B over machine A by as great a margin in another. This paper purposes to identify some of the more prominent reasons why this is so,

Jan 1, 1944

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956