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By N. Lilienberg

During the past fen- years, the requirements for steel have been raised so high that soundness is more important than ever before. The old practice mas to make steel ingots of suffciently large sections to permit a considerable reduction of area in rolling and hammering to a given size, relying on the fact that by such rolling and hammering all cavities will be squeezed together and practically eliminated. The finished sizes, if found by inspection of the surface to be faultless, were therefore pronounced to be sound. But when such steel is " worked up," the manufacturer is surprised and disappointed to find that it splits, or that streaks and seams make the product unmarketable. Large sections, such as rails, beams or heavy forgings, may, within certain limits, be sufficiently strong, even if the sides of the cavities are only squeezed, and not welded, together. But it is well known that, in the interior of heavy articles, under certain conditions, forging may develop small streaks into large cavities. Small sections, steel for ordnauce and tubes, and numberless articles in the tool-trade, always show up the defects. It may be doubted whether cavities in steel ingots can ever be completely welded. The old theory is, that the silver-clear blow-holes, without the blue oxide, can be welded by suffcient working. They are, however, not empty, but are filled with carbonic oxide. It is admitted that the " blue " cavities, resulting from air mechanically drawn down into the mold during the casting, can never be welded, because the oxide does not melt, and there would be no escape for it if it did. The only way in which steel can be made satisfactory for the above-named particular purposes is by having it " dead molten." But then the trouble of piping is encountered. As is well known, a pipe is the result of the contraction of the liquid interior after the surface of the ingot has become solid by contact with the mold. When this contraction is partly

Jan 1, 1907

By G. C. Bateman

THE Workmen's Compensation Act of Ontario was passed in 1915 and Miners' Phthisis was added to the list of compensable industrial diseases in 1916. Under this provision of the Act only about two cases were compensated per year. In 1924, The Department of Public Health made a survey of miners in the four principal camps-Sudbury, Porcupine, Kirkland Lake and Cobalt-and the survey indicated that an alarming proportion of the men exposed to dust had silicosis in one or other of its several stages. A number of conferences were held between representatives of the Department of Mines, the Department of Public Health, the Compensa-tion Board and the mine operators. The operators were advised that in the earliest stages of silicosis there was no physical disability and if men in that stage were removed froni underground there would be little danger of permanent disability. They were further advised that if active steps were taken at once to compensate men that had some real disability and remove from the mines men in the early stages of silicosis, the first cost would be the greatest and thereafter their liability should decrease. As a result of this advice, and having at that time no reason to doubt the findings of the survey, the operators agreed to do all that was asked of them and cooperate with the Government in the steps believed neces-sary to meet the situation, and to provide compensation for the men affected.

Jan 1, 1937

By John A. Von Essen

To some, the paddle mixer may seem old as antiquity. Yet, as industrial mixing requirements become increasingly sophisticated in the late 20th century, it is proving more useful and versatile than ever. From water treatment applications to high-pressure reactors, the new and specialized demands in mixing have been met by a continuous evolution and adaptation of this basic workhorse design.

Jan 7, 1978

By Charles H. Snow

In vol. xxxviii. (1889) of the American Journal of Science, under the heading " Pseudomorphs of Native Copper after Azurite from Grant County, New Mexico," Mr. W. S. Yeates describes a most interesting mineral form. His account is, that a material having the appearance of native copper, but brittle and much lighter than native copper (its specific gravity being but 4.15), was submitted to him by the United States National Museum for examination. The substance was reported to him as occurring in masses, varying in weight from one ounce to seventy pounds, and composed of tabular crystals, variously grouped. The specimens, when submitted, ex hibited on the outride a covering of clay; and they were subse quently found to consist of particles of the same clay, intimately mixed with others of native copper, producing the aspect, without the weight, of pure copper. The forms of the azurite crystals, found at Bisbee, Arizona, having been suggested by the specimens, actual goniometer-measurements were made; and the two crystallizations were thus proved to be identical. To these statements I may be permitted to add some further in formation, derived from personal examination, and illustrated with a suite of characteristic specimens collected by myself (Fig. 2).* Grant County, New Mexico, in which these specimens were found, is a region noted for variety of mineral species. The sixth edition of Dana's Mineralogy mentions many of the silver, copper, and lead minerals, and also turquois, aragonite, wulfenite, barite, fluorite, vanadinite, etc. I have noticed also green and red garnet, molybdenite, native alum, smithsonite, bornite, etc., some of which presented peculiar modes of occurrence. The green garnet, for instance, was in masses formed of separate crystals, each of pea-size and not unlike that vegetable in tint and smooth opaqueness. The crystallization was

Jan 1, 1893

By J. G. Koenigsberger

THE electrical specific resistance of rocks in the field is measured by sending a current through a medium of great volume, compared to the electrodes, whose resistivity should be measured. The whole resistance can be determined by the Wheatstone bridge and the specific resistance calculated by a well-known formula. The resistivity of some rocks in place in Germany and in Switzerland is given; first, of a rock near the surface, and especially near electrodes. Practical applications are made in the determination: (1) of the continuity of a conducting orebody; (2) of the surface area of an orebody; (3) in the detection of a water-bearing fault in a salt mine. Preliminary observations are described: (1) on the influence of the depth of ground-water table; (2) on the detection of gas under high pressure in coal seams. The observations in this paper of the electrical resistivity of rocks and soil in place are along the lines of the very interesting method and results of the Messrs. Gish, Rooney, Hotchkiss and Fisher.1,2 All the work described has been done since 1920.

Jan 1, 1928

By John F. Walker

WITH an estimated production of over 936,000,000 for the first six months, the gross value of mine production for 1937 in British Columbia should exceed $70,- 000,000. This figure, if attained, will establish an all-time record for the Province. Great changes have taken place in the different divisions of the mining industry since 1929, the previous peak year of mineral production. A brief review of the earlier history of mining in the Province will also be given.

Jan 1, 1937

By H. J. Seaman

The cost of keeping platinum ware in repair becomes such an important item in laboratories where much fusion-work is done, that a method of saving in this direction may not prove unacceptable to at least some of the members of the Institute. Some two years since I had the misfortune to puncture an almost new Bishop crucible. As an experiment I endeavored to patch it, and with such success that it is still in constant use. This may be accomplished in the following manner : The crucible and patch, which should be of stout foil, are rubbed bright with silica, or rotten-stone; a light platinum wire, welded to a corner of the patch, and the whole treated for several hours with hot concentrated hydrochloric acid; after which they are thoroughly washed with distilled water and dried. The head of an ordinary iron rivet, 4 inches by $ inches, is rounded off by hammering to somewhat the shape of the crucible. This is sunk 2 inches in a block of hard wood, and firmly wedged in place. This serves for an anvil. The hammer is an ordinary cast-iron toy, 11/2 inches long, and # inches in face, mounted on a 4 inch iron rod, 10 inches long. A gas-blowpipe is fixed in a horizontal position, and the strongest heat obtainable with it directed upon the rivet head; this soon at-

Jan 1, 1885

By J. P. Sheehan, W. R. Hibbard, M. Baeyertz

This paper deals with molybdenum modifications of 5140 steel that have the same hardenability but a better tolerance for phosphorus than the AISI-SAE 5140 grade. Lack of toughness in steels with higher than normal phosphorus contents is well known to metallurgists. This problem is troublesome even within normal phosphorus ranges, if the heat treatment or the design of the part or the service is critical. Under such unfavorable conditions and also in the case of phosphorus contents toward the upper side of the commercial range, the use of molybdenum to replace a part of the chromium in 5140 steel provides a factor of safety. The toughness of steel is variously exhibited in different mechanical tests; broadly the term is applied to the capacity of the steel to deform prior to fracture. Defined in this way, toughness is considered to be an inherent quality that depends upon the composition and structure of the steel, and also upon its temperature during deformation and fracture in the test. In the present state of our knowledge, the type of mechanical test needs to be included in any discussion of toughness, because the revelation of this quality in steel depends on the stress state and rate of stressing imposed by the test. In comparing the toughness of one steel with another by laboratory testing, it has long been customary to use notched tests that impose severe constmint to deformation, and then to test over a range of temperatures to obtain the so-called transition. At temperatures above the transition, the steel fails after considerable deformation and absorption of energy. Below the transition, less energy is absorbed as the steel fails largely by cleavage. The transition range itself is characterized by a more or less abrupt change in energy absorption and type of fracture. The conventional V-notch Charpy impact test has been used exclusively in the work covered by this report. For the steels under study, rather sharp transitions are obtained with this test, at testing temperatures that are easily obtained in the laboratory. The position of the transition on the testing temperature scale provides a rather sensitive index of the toughness of the steel, when the steels under study are similar in character as they are in this work. Turning to the metallurgical reasons for the greater toughness of one steel as compared to another, the authors propose to limit the discussion to the small field under study. Only one structural state is considered, tempered martensite of a hardness of about 28 Rockwell C or 269 Brinell. The study deals first with the loss of toughness in AISI-SAE 5140 steel caused by increasing the phosphorus content from about 0.020 to 0.040 pct. A second part of the work deals with counteracting this loss in toughness by replacing a part of the chromium by molybdenum. A series of molybdenum modifications was studied, in each of which the chromium was reduced sufficiently to duplicate the hardenability of 5140 steel. Phosphorus affects the toughness of steel in two ways. An inherent lack of toughness of phosphorus-bearing ferrite as compared to low phosphorus ferrite has often been noted. Jolivet and Vidall have shown that phosphorus has the same effect in tempered martensite in chromium steels. The other well known effect of phosphorus is to make steel susceptible to temper embrittlement. Temper brittleness is a loss in toughness brought about by tempering steel within a limited temperature interval somewhat below the A1 temperature. In most of the standard AISI-SAE alloy steels, this temperature interval is approximately 850-1100°F. Either of these types of loss in toughness is easily followed by the shift in the transition temperature obtained with the notched-bar impact test. The data to be presented show the beneficial effect of substituting molybdenum for a part of the chromium in 5140 steel with either moderate (0.020 pct) or high (0.040 pct) phosphorus contents. Both the inherent lack of toughness of phosphorus-bearing steel and temper brittleness are counteracted by this use of molybdenum. The work of Jolivet and Vidal mentioned above shows the detrimental effect of phosphorus on the toughness of tempered martensite in the absence of temper embrittlement, as well as the temper brittleness caused by phosphorus. They used two steels, essentially 0.25 pct C-1.4 pct Cr, with 0.044 and 0.013 pct P, respectively. The nonembrittled state was obtained by quenching in oil from 1610°F, then tempering for one hour at 1200°F and quenching in water. In this state the transition temperature range of the low phosphorus steel in the notched-bar impact test was below that of the steel with 0.044 pct P. An additional treatment of 24 hr at 975°F (that is, in the embrittling range) caused both steels to lose toughness, but the high phosphorus steel showed the greater embrittlement. Recently Hollomon2 has published a comprehensive survey and bibliography of the literature on temper brittleness, to which the reader is re-

Jan 1, 1950

By W. C. Krumbein

GEOLOGICAL problems are approached from a geometrical (space relations) viewpoint, a kinematical (time sequence) viewpoint, or a dynamical viewpoint. The first two require sound training in conventional geology and in field methods. The third approach requires a solid foundation of chemistry, physics, and mathematics. Modern training for geologists should include close integration of basic sciences with geological principles. INTRODUCTION Our knowledge of the earth has increased tremendously during the last half century. We know more about its surface configuration, the distribution of its natural resources, the procession of living forms that inhabited it in the past, the chemical composition of its oceans, the areal distribution of its surface rocks, the movements of its atmosphere, and so on. Not only do we know more facts about the earth, but we have a better understanding of the processes that take place on and within it, such as the nature of earthquakes, the thermodynamics of the atmosphere, the chemical equilibria involved in the formation of igneous rocks, the mechanics of stream flow, the dynamics of the earth's origin, and so on. Many sciences contributed to the sum total of this knowledge, including such established disciplines as geology, geography, physics, chemistry, astronomy, biology. Out of this accumulation of new knowledge grew also a group of new sciences, such as seismology, oceanography, meteorology, volcanology, hydrology. Collectively these latter are known as the geophysical and geochemical sciences, and to a large extent they began as branches of geology. Until the turn of the century, for example, the study of earthquakes (seismology) was a part of geology, although as early as 1846 Mallet, a physicist, had suggested that the subject could be investigated by elastic-wave theory. Comparatively little progress was made along these lines until the seismograph was developed near the turn of the century; since then, additional earthquake data have accumulated rapidly, but more important, the interpretation of these data essentially has kept pace with their accumulation. In similar fashion, meteorology, was generally considered a branch of geology as recently as one or two decades ago. Considerable progress had been made in such aspects as weather forecasting, but the science dates its recent rapid rise from the year 1911, when Bjerknes first applied the principles of dynamics to the analysis of air masses. The rapid development of such disciplines as oceanography, volcanology and hydrology was due in part to the application of principles of chemical equilibrium, of dynamics, and of thermodynamics to earth problems, by men who were essentially physicists or chemists by training. The last half century, therefore, and particularly the last two decades, saw the influx of numerous chemists and physicists into the realm of the earth sciences. In the meantime the main body of geology itself showed a marked growth, and

Jan 1, 1941

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By W. N. Lacey, B. H. Sage, J. S. Billheimer

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By Alexandre Pourcel

The perusal of Mr. Willard P. Ward's " Notes on the Behavior of Manganese to Carbon," presented at the Washington meeting of the Institute in February, 1882, has suggested further reflections on the same general topic, and has led to the preparation of the present paper. The same observation that Mr. Ward has put on record in his "Notes" was also made by myself at about the same time (in August, 1875), and under almost the same conditions. From a blast-furnace that was very hot, as was the furnace mentioned by Mr. Ward, I obtained a pig-iron containing about fifteen per cent. of manganese, gray in color, and very tough. It could be pulverized, but could not be cut with the chisel. I analyzed this iron and found that it contained, as I had suspected,a large amount of silicon. From this fact I drew the conclusion that the silicon had deprived the manganese of its power of dissolving carbon, since the latter, instead of occurring in the pig in combillation, appeared as graphitic carbon. I thus saw reproduced on a large scale, and demonstrated in a visible way, the property that Colonel Caron, a French scientist, had discovered in silicon,—the property of obstructing the process of hardening in steels by keeping the carbon in the graphitic condition. An attentive study of the conditions under which the phenomenon observed by Mr. Ward takes place led me to go back to operations of synthesis, and to make as I wanted them pig-irons containing varying quantities of silicon, manganese, and carbon. An iron, thus prepared, was intended to serve me as a chemical reagent in the production of steels cast without blow-holes, such as my lamented friend, Mr. A. L. Holley, has introduced and made known to the United States. What I needed in order to make very soft steels, cast without blow-holes, was an iron which, when it was added to the bath of steel, introduced into the bath a sufficient amount of silicon and of

Jan 1, 1883

By J. F. Myers

A bit of old philosophy: The optimist, the pessimist, The difference is droll; The optimist, the doughnut sees, The pessimist, the hole. This is a neat summation of the viewpoint of those engaged in "treating the crude mineral crust of the earth." Many of those in high places have reminded us during the year of the diminishing supply of the resources so essen-

Jan 1, 1948

By Ronald R. McNaughton

The most recent group of papers on the general subject of lead smelting were published in AIME Transactions, vol. 121, in 1936. The lecture deals with changes which have taken place in the Past 30 years in this industry. The subject matter covers the essential steps of charge preparation, sintering, blast furnacing, dross treatment, refining, and slag fuming together with the subsidiary or associated activities of analytical procedures, dust and fume collection, maintenance, and hygiene. IN 1936 the AIME published Transactions, vol. 121, entitled "Metallurgy of Lead and Zinc". In the preface to this volume the chairman of the Committee on the Reduction and Refining of Lead and Zinc, Carle R. Hay ward, said in part: ... since the World War few papers of major significance have appeared on the production and refining of lead and zinc, although many improvements in technique have been made, which have attracted little attention because they were merely developments of existing practice. Other changes of a more radical nature have also been made, but... they have been given little publicity. It seems appropriate, therefore, at this time that the AIME should sponsor a volume on lead and zinc metallurgy... . That the publication of this compilation was timely is attested by the rapidity with which the surplus stock was depleted. It has now become a collector's item. Although a comprehensive monograph on the occurrence, extraction, refining, and uses of zinc was published by the American Chemical Society in 1959,' one could almost repeat Professor Hayward's words to describe the present situation in the literature of lead reduction and refining. So it is my intention today to discuss briefly some of the changes and improvements which have taken place in the metallurgy of lead in the interval since the publication of vol. 121. The lead blast furnace, which made its appearance in America about 1870, is still dominant in the reduction field. However there are other reduction methods in use today in special situations. In those rare circumstances where the material to be treated is very high grade, consideration might be given to the Bolidens electric furnace method2 or the Lurgi self-fluxing process3 or possibly to the rotary ore hearth. Each of these latter three processes makes use of the roast-reduction reactions with the result that fuel require-

Jan 1, 1969

By E. R. Gilliand

KNOWLEDGE of a large number of the physical properties of the hydro-carbons is needed in the calculations and studies of the production engi-neer. Since experimental data on these properties of the individual hydrocarbons and their mixtures are available in only a relatively few cases, the use of generalized correlations has developed rapidly in the last decade. The generalized correlations of pressure, volume and tem-perature,1 enthalpy,2 and vapor-liquid equilibria,3 on the basis of reduced temperatures and pressures, are outstanding examples of this develop-ment. These correlations are of particular value to the production engineer interested in the flow of oil and gas, since they can be used to estimate the conditions under which segregation of phase occurs as well as the composition, density, and relative amounts of the phases. The technique of using the correlations for such estimations has been pub-lished by several authors¢ and will not be considered in this paper. A considerable number of data have been obtained to check the generalized pressure-volume-temperature correlations, and these data indicate that such relations hold for the hydrocarbons from methane to heptane. The accuracy is in general sufficient for most engineering pressure-volume-temperature calculations. However, the generalized correlations of enthalpy and vapor-liquid equilibria have in general been developed from the pressure-volume-temperature correlations by thermodynamic calculations and only a relatively few experimental data are available to check these calculated values. The calculations from pressure, volume and temperature are likely to lead to large errors in the calculated enthalpy and vapor-liquid equilibria. Thus, in the calculations of enthalpies, slopes of the pressure-volume-temperature data are employed, and determining these slopes can greatly amplify small errors in the original data. In the vapor-liquid equilibria calculations it is necessary to have the pressure-volume-temperature relations of the mixture, and the latter properties are much more questionable than those of pure components, particularly in the critical region. A considerable number of experimental data are

Jan 1, 1939

By G. Borelius

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

Jan 1, 1952

By George E. Kruger, William F. Butler

The less developed nations maintaining a free enterprise economy (to which this chapter is addressed) have real and substantial opportunities to lay a foundation for general economic progress by using their mineral resources. Most of these nations have mineral resources which could be developed. By seizing these opportunities, nations seeking rapid economic development can secure a source of foreign exchange earnings to finance the imports needed for growth and, at the same time, increase the technical knowledge and well-being of an important part of their population. History clearly shows the manner in which most of the currently industrialized nations have used mineral resources to support their development. Indeed, few nations have managed to achieve a high level of income without a firm base of mineral resource development. The main exceptions appear to be the Netherlands, Switzerland, Denmark, and New Zealand, and the last two have based their prosperity on a highly efficient agriculture. Economic growth in the United States, the United Kingdom, Canada, France, Germany, and Russia was importantly based on the use of indigenous mineral resources. Despite this record of accomplishment through mineral development, many of the currently less developed nations are not taking advantage of the opportunities available in the mineral field. Restrictive laws or practices in many such nations operate effectively to prevent development of mineral resources. This failure to grasp real opportunities for development is based on a series of arguments that the mineral field offers few substantial and attainable advantages. Among these, the following propositions appear the most important:

Jan 1, 1964

Prof. Henry M Howe, New York: It is extremely probable that this efflorescence of silica is due to the liquation either of silicon or of a silicide, and the subsequent oxidation of the silicon to silica. As Mr. Fackenthal says, it is very hard to see why silicon should liquate from an iron containing so little silicon, and it seems more probable that some silicide of some volatile element has liquated, and has dissociated on reaching the air, and that the volatile element has volatilized, leaving the silicon to oxidize to silica. The volatile elements present which might thus liquate in combination with the silicon are sulphur, zinc, and lead. It is hard to see why sulphide of silicon should have liquated from an iron containing so little of either sulphur or silicon. At first, one naturally thinks that either the zinc or the lead present in this furnace might have liquated as silicide. It is true that they are both volatile at the temperature within the furnace, but then the vapor-tension* of each of them within

Jan 1, 1901

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.' The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962