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By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Willard P. Ward

I DESIRE to put on record a fact in relation to the effect of manganese on pig iron which I have never seen in print, and which may, perhaps, not have been observed by anyone except myself. In 1875, while experimenting on the production of ferromanganese in a blast furnace, I had burdened the furnace with a charge which I calculated would produce a 15-per cent spiegel. The furnace was very hot, having been running for a couple of days on a very light burden, and making a burnt iron, preparatory to the experiment I proposed to make to produce a high grade of spiegel. I calculated that the charge would begin to work in the furnace in about twelve hours after it was put on. After the lapse of that time I commenced to watch the furnace carefully, but found little or no. change in the appearance of the metal, although there was a very decided change in the cinder, showing that the manganese ore had come in work. The iron was quite gray and very tough. The character of the cinder was good for a spiegel cinder, and I could not imagine where the manganese was going to, as it (lid not appear to be in either metal or cinder in anything like the quantity indicated by the charge. The next morning things were still in, the same condition. The furnace was very hot, the cinder good, and the iron very gray. I was then sorely puzzled. I had never heard of a gray iron with over 4 or 5 per cent, of manganese, and had no notion that an iron with more manganese could be gray and tough. With great difficulty a piece for chemical test was broken from a pig. Not less than a hundred blows from a heavy sledge were required to break it off I took the specimen to the shop and directed that some borings from it should be brought to the laboratory, as soon as possible, whither I myself at once repaired -to put things in readiness for a rapid manganese determination. In about half an hour the machinist came in with the iron specimen in one hand and about, a dozen blunted and broken steel drills in the other, saying that it was impossible to drill the iron. There were several little depressions in the iron, which was malleable enough to be indented by the point of the drill, but not a chip had been cut from it. The metal was never subjected to further physical tests. A chip broken from

Jan 1, 1882

By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world's cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By Edwin M. Chance

During the last decade many conditions have been encountered that have materially increased the cost of the production of coal. As in most cases it has not been practicable to increase the selling price of such coal sufficiently to insure the necessary margin of profit, the mine management has been forced to avail itself of what might be termed unusual means that costs might be held at as low a figure as possible. The so-called efficiency engineer has been called upon, costly power plants have been built and machinery has been installed to replace manual labor wherever possible. Another aid used recently to secure economies through the more intelligent production of coal, is the chemist. As the coal industry, barring the production of byproduct coke, does not at once give evidence of its need of the services of the chemist, the writer will endeavor to point out a few of the services that this branch of the staff has been able to render. The preparation of coal in the past has been carried on entirely upon an empirical basis, that is, the criterion adopted has been an ocular inspection. Unfortunately, the appearance of a coal and especially of an anthracite, has but little relation to its fuel value, and as long as coal is purchased for the heat that can be obtained from it by its combustion, the quantity of such heat that is purchased must be one of the principal desiderata in selecting or preparing a coal. Were coals purchased for use as bric-a-brac or for exhibition in museums it might be both wise and just to purchase them upon their appearance. After 4 or 5 years of investigation the fact has been established that coals of very inferior appearance, and I now have special reference to anthracite, might and often did possess heating and burning properties superior to those possessed by bright coals which in the past had commanded considerable and uniform premiums in the market. This being the case the question arose as to whether the trade could be convinced of this fact. While at first some difficulty was experienced in establishing the quality of such dull coals, still it was found that the real obstacle to the sale of these materials in the past had been the fact that the coal producers' own sales departments felt convinced of the inferiority of this type of fuel and when complaints were registered they were given ready credence. Upon convincing the sales department of the quality of this type of fuel, but

Jan 1, 1917

By Emby Kaye

IT is the purpose of this paper to outline briefly some of the considerations that enter into the economics of so-called recycling, the generic designation of the relatively recently developed process by which a condensate† is separated from gas-distillate gas at high pressure and the residual gas returned to the reservoir. This subject necessarily embraces not only a discussion of factors that should be considered in projecting a recycling operation, such as estimating reserves, investment and operating costs, but also a comparison of condensate with other types of petroleum. The place of condensate in its relation to the total supply of crude oil is pointed out as well as certain logical methods of product disposal. The cost of drilling wells and lease maintenance is not pertinent to this discussion because income and revenue are in this paper confined to that retained by the plant or plant operator for supplying processing facilities for the gas. Before the development of recycling a great many gas-distillate gas fields in Louisiana and. Texas provided no income to their owners. When gas was sold from these reservoirs it was accompanied by irretrievable losses of condensate in the formation. The understanding of the function of retrograde condensation resulted in the introduction of a new commercial petroleum recovery process for these hitherto unexploited fields and now permits the conditioning of this type of wet gas field for the sale of dry gas therefrom without waste. SOME ECONOMIC FACTORS The study of a gas-distillate field for possible exploitation necessarily involves the critical appraisal of a number of elements, chief of which will be discussed here: (I) estimate of distillate in place, (2) estimate of distillate that can be brought to the surface, (3) available market, (4) costs. The considerations affecting the estimating of distillate reserves. in place are in the main subject to the same errors as are involved in determining dry gas reserves. Determinable data including acreage, sand thickness, reservoir pressure, reservoir temperature, porosity and connate water provide the basis for calculating the volume of gas in place. Ample allowance must be made for connate water, which may occupy from 20 to 35 per cent of the pore space of the sand. The factor of supercompressibility is to a considerable extent nullified by the reservoir temperature. It has been considered well advised to allow this factor to serve as a cushion. With the gas reserves calculated, it remains only to assay the distillate content of the gas. Those familiar with the handling of "wet" gas at high pressure readily appreciate the variables in sampling gas from

Jan 1, 1941

By R. S. Lewis

IN a recent study1 of the evolution of engineering education 1870 was taken as the initial point, as it is said to mark the transition from the poineer era in American engineering education to an era of rapid growth and consistent development. Prior to the founding of Rensselaer Polytechnic Institute in 1824, West Point Military Academy was the principal source of formal engineering training. In 1849 Rensselaer revised its program on the model of the leading French technical schools. Lawrence Scientific School was estab-lished at Harvard and Sheffield Scientific School at Yale in 1847. The University of Michigan pioneered in en-gineering instruction in the West, offering its first course in 1853 and awarding its first degree in 1860. Other important steps in -the progress of engineering education were the founding of Columbia School of' Mines in 1864, the opening of Massachusetts Institute of Technology in 1865, and the founding of Cornell Uni-versity and the Thayer School of Civil Engineering at Dartmouth in 1867. From its organization in 1852 until 1871 the Ameri-can Society of Civil Engineers was virtually the only national society of engineers. In 1871 the American Institute of-Mining and Metallurgical Engineers was founded, to be followed later by the Mechanical En-gineers in 1880 and the Electrical Engineers in 1884. This expansion and diversification of the engineering profession was paralleled in the colleges, and by 1885 the plan of different curricula in the major branches of engineering was soundly established.

Jan 7, 1927

By A. U. Seybolt

RECENTLY, cases of coexisting ordered and disordered phase equilibria have been reported among face-centered cubic metals,1"3 but not on body-centered cubic systems.4 McQueen and Kuczynski5 showed a single line as the boundary between ordered solid solution of Fe3Al type and corresponding disordered solution in the Fe-A1 phase diagram based mainly on dilatometric and magnetic measurements. Such a single line would indicate a second or higher order transition. or an absence of coexisting order and disorder. The writer found previously a two-phase equilibrium region at 800°C consisting of ordered and disordered solid solutions of Fe3Si in a matrix of approximately 1-6 wt pct Si (Fe3Si is of 14.3 wt pct Si). A similar two-phase region of ordered and disordered Fe3Al solid solutions might be expected if the similarity between Fe3Si and Fe3Si structures hold true. In the present investigation, a wire of 22 at. pct Al, balance Fe and 0.0513 cm in diameter was subjected to electrical resistivity measurement in vacuum as a function of temperature between 300 and 800°C, see Fig. 1. There was excellent agreement between data taken on heating and on cooling: no hysteresis was observed. The Curie temperature was determined to be 640 °C which agrees with the finding by McQueen and Kuczynski.5 But in addition, there were two transitional points in the resistance-temperature plot at 510oC and 400 "C. The former is thought to be a connection with the transition from disordered state to a coexisting order and disordered equilibrium state; while the latter, from such coexisting state to ordered state. Fig. 2 shows a phase diagram where the suggested two-phase region lies between dotted lines. The solid lines are those of McQueen and Kuczynski.5 Since these authors found only a single-phase boundary between ordered and disordered Fe3 Al, it would seem likely that the dilatometric method used by these authors was not sufficiently sensitive to resolve the ordering reaction into the two-phase boundaries. In addition, their phase diagram conflicts with the statement they make on P. 1 of their paper: "The sharpness of the peaks indicates that ordering to Fe3A1 is a first order reaction." The suggestion of coexisting order plus disorder in Fe3A1 must be considered tentative until confirmed by high-temperature X-ray examination. If

Jan 1, 1961

By A. Sutulov

The segregation process, an alternative to benefi-ciation of oxidized and mixed sulfide-oxide copper ores, is studied here with particular emphasis placed on time, temperature, and coke and salt percentage factors. The results show that in a segregated charge, the copper assay of the coarsest fractions normally is of the same order as the copper assay of the tails obtained from grinding and flotation of the same charge. This observation suggests the possibility of limiting or even eliminating the grinding step from the flowsheet of a segregation plant. The segregation process, which offers an alternative to beneficiation of oxidized and mixed sulfide-oxide copper ores, was discovered in 1923 by Moulden and Taplin1,2 who were attempting to apply the Perkins process3'4 to a Chilean ore from the Sagasca mine. After a number of investigations and pilot plant tests,'-' the segregation process became a successful industrial operation.'r9 The process aroused considerable interest in Chile because of the existance of large reserves of oxidized copper minerals which could not be treated by conventional hydrometallurgical methods because of the high consumption and prohibitive cost of sulfuric acid. During the last two years, the Mineral Dressing Dept. of the Institute de Investigaciones Tecnology cas of University of concepci6n (Chile) has carried out a test program on 23 different ore samples representative of the national territory. These tests were carried out on a semi-continuous and batch scale with a rotary, automatically controlled and gas-fired furnace (supplied by Bartlett and Snow, Fig. 1). The results of these tests indicate that out of the 23 samples 20 can be successfully treated by this process with recoveries of copper ranging from 85 to 95%.10,11 The purpose of this paper is to treat some specific problems related to the segregation process. TIME AND TEMPERATURE FACTORS Time and temperature of calcination play an important role in the segregation process. When moderate salt and coke conditions were maintained (each of reagents was added in the quantity of 1 — % wt), systematic testing easily demonstrated the influence of these two factors on segregation and flotation recovery. The pertinent results are summarized in Fig. 2. To determine what specific changes the segregation process made on the ore, the samples, segregated at 700°C for different periods of time and under standard conditions, were granulometrically analysed and

Jan 1, 1963

By J. T. Ryan

SiR Humphry Davy's epoch-making treatise delivered on Nov. 9, 1815, before the Philosophical Society of London, first announced and demonstrated a flame safety lamp for detecting methane in mine air. Coal mining was known in England as early as 1180, more than 600 years before the advent of a safe lighting and gas-detecting appliance. Mining, no doubt, took place first in outcrop coal, and danger from gas did not become apparent until the workings became deeper and more extensive. Davy's lamp did much to increase the safety of miners, and a modified Davy lamp is still widely used for detecting the presence and approximate amount of combustible gas in mine air. No factor in coal mining has improved more rapidly during the past 15 years than safety measures. This progress came about not only as a result of the workmen's compensation laws now in force in most of the states of the Union, but because the research work of the U. S. Bureau of Mines had demonstrated some dangers incident to coal mining which were not considered to be serious matters prior to that time. Electric power and explosives are necessary but potential hazards in American coal mines. A general mechanization program is now under way, while the mines are growing deeper and more extensive. Consequently ventilation problems are more complex and a demand has been created for positive detecting devices for carbon monoxide as well as methane. Scientists and manufacturers, working hand in hand during the past 10 years, have invented and developed appliances which make systematic and effective examination of mine air possible. The object of this paper is to describe briefly the approved testing devices in use today, with the hope that they may lead to the saving of life. Two Groups of Dangerous Coal Mine Gases Dangerous coal mine gases may be placed in two groups: (I) those that are dangerous because of their explosive properties, and (2) those that are dangerous because of their toxic properties. Methane (CH4) is the important gas of the first group, and in so-called gaseous mines constantly exudes from the coal and rock; it may accumulate and form an explosive mixture. The explosive range of methane-air mixtures is well defined. The low limit is 5 per cent., the high limit 15 per cent., and the most explosive

Jan 1, 1927

By M. P. Sidorova, D. A. Fridrikhsherg

The surface charge, electrokinetic potential and surface conductance were studied for silica, alumina and rutile as the functions of PH and concentration of 1-1 electrolyte solutions. The adsorption potentials of potential-determining and specifically adsorbed ions were calculated from isoelectric and zero charge points on the basis of Stern equation and thermodynamic description. From surface conductance and charge data the mean ionic mobilities in double layer were estimated. The results give some information about the real structure of oxide-electrolyte interface and gel-layer concept.

Jan 1, 1980

By S. G. Lasky

Abraham Lincoln is reputed to have said that if you want to chart a course to some destination, you have to know where you are starting from. In this instance we have to define our starting point in a double manner: 1) What was the theoretical basis of the Paley predictions? 2) What actually did the Commission predict, so that we can see how the predictions have worked out up to now as a basis for considering how they may have to be changed.

Jan 3, 1960

By C. W. Hoffman, W. R. Hinken

Probability sizing, a fairly recent development in the field of particle separation, is now under investigation to determine its value to the mining industry. The method employed is probability sizing through a vibrating network of decreasing screen openings. While probability sizing is not new, the possibility of using it for coarse, highly abrasive ores at high tonnage rates has only recently appeared to merit practical consideration. The advantages of probability sizing vs. conventional screening methods are: (1) reduced space requirements for a high capacity unit, (2) fewer moving parts, (3) more versatile product sizing selection, (4) reduced maintenance requirements, and (5) lower power consumption. Screening is a necessary part of virtually every crushing circuit. At some stage in the process, particle separation becomes a controlling factor in the operation. The basic type of screen in use today is the vibrating unit, which usually employs a mechanical vibrator of one type or another to obtain sizing and material transportation across the screen surface. The vibrating screen has its limitations and inherent problems. Operators must live with: (1) high maintenance — worn rods, screen cloth, spacers, cross members, chutes, etc., (2) low capacity in relation to floor space requirements, (3) extreme noise levels, (4) high power consumption, and (5) structural problems in the screens and supporting steelwork. All plant operators have become tolerant of these drawbacks through the years, and little innovation has been developed in screening. The vibrating screens in use today incorporate improved metals, more efficient power sources, better lubricants, and increased manufacturing skill, but the basic machine itself remains unchanged. Screening is a relatively small part of most plants' operating expenditures and gets relatively little attention from research and development. The HiProb sizer is a new approach to the problem of particle separation on a high tonnage basis. Developed by Dr. Fredrik Mogensen (president of Fred-rik Mogensen, A. B. of Djursholn, Sweden), this unit has found its primary acceptance in the sizing of wet or dry materials in the fine ranges. Climax has been working cooperatively with Mine and Smelter Supply Company, the United States licensee, on the adaptation of the sizer to obtain consistent recovery at a high tonnage rate on a — 3/8-in. separation. This was a new application for the sizer and opened up a whole new field of problems. Dr. Mogensen's machine utilizes the control of normal probability of falling particles and is designed to eliminate some of the undesirable features of vibrating screens mentioned earlier. The machine is light, compact, consumes less power than conventional screens and has a low noise level. PRINCIPLES Probability sizing is a process designed to allow solid particles to segregate with a high ratio of the materials reporting into their respective size fractions with a minimum amount of misplaced particles. Sizing is defined in this paper as segregation of dry solid particles into fractions of comparable sizes. Probability is usually estimated as the ratio of the number of ways an event might occur vs. the total number of allowable ways. The probability process described depends upon the fact that particles falling through a network will segregate across the sizing surface even though all openings are larger than the particles. The degree of segregation is dependent upon the particle size and the trajectory applied by the sizing network to each falling particle. Specifically, the process utilizes a maze made up of screen cloth to control the path of a particle in free fall as illustrated in Fig. 1. The usefulness of this probability sizing process is dependent upon the degree of efficiency of an effective maze. Primarily, a maze must be extremely flexible to meet the multi-faceted nature of solid particles and, at the same time, the degree of control must be reproducible so that a desired separation is predictable. Dr. Fredrik Mogensen has formulated a maze that is not only flexible and easily controlled, but, mote importantly, easily adaptable to a working machine.

Jan 1, 1970

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

Discussion of the papers of Benjamin Talbot. E. A. Beck, Emil Gathmann, Sir Robert A. Hadfield, and P. H. Dudley, presented at the New York Meeting, February, 1913, and printed in this Bulletin (No. 76, April, 1913). CHAIRMAN JAMES F. KEMP :-I call upon Prof. Albert Sauveur to open the general discussion on the subject of sound steel ingots. ALBERT SAUVEUR, Cambridge, Mass. :-I believe that I have the privilege, this instant, of opening one of the most important, significant and far-reaching discussions ever held before this Institute. I believe that our talk this morning will be heard far and wide, not only on this side of the water, but also on the other side. Everywhere, in short, where steel is manufactured. I welcome the opportunity of expressing my mind in regard to the production of sound steel ingots, a subject about which I entertain some very decided opinions. I shall not attempt to discuss the relative merits of the various processes that have been described. I shall, on the contrary, confine myself to a general consideration of the important questions before us. So intensely do I feel regarding the production of sound steel ingots that I have put my remarks on paper in my desire to present my Views.

Jan 4, 1913

By David V. Ragone, Richard E. Balzhiser

The liquidus uranium concentration in the U-Bi system is given by the following expression for the temperature range 400° to 800°C: No break was observed in the curve over this temperature range. The partial molar enthalpy change for uranium in the liquidus reaction, UBi2— U + 2Bi, was found to equal 12,300 cal per g mole. Copper produced a continuous decrease in the liguihs uranium concentration at 600°C. The presence of copper in the solvent was observed to affect the uranium activity coefficient according to the following expression: duced no change in the liquidus combosition below 0.6 at. pct Pd. Higher palladium concentrations sharply depressed the uranium concentration. SOLUTE behavior in molten alloys has been shown to be strongly influenced by the presence of additional species. Much attention has been given to such phenomena in iron-base systems where a number of alloying elements and/or impurities are likely to be present in small but significant quantities. Frequently, the interaction of these solutes has altered their thermodynamic behavior to the extent that reaction equilibra are appreciably influenced. Consequently, much of the information available for binary behavior must be reevaluated when additional components are likely to be present. Similar interactions can be expected to occur in bismuth-base solvents. Interest in the use of bismuth solutions of uranium as reactor fuels has stimulated investigators to explore the effect of various elements on the liquidus uranium concentration. Criticality requirements necessitate close control of the uranium concentration which, at the anticipated operating temperature of 500°C, approaches saturation. Consequently, elements which suppress the liquidus concentration could produce serious reactivity problems. Since the fuel solution is cer- tain to contain additives, such as magnesium and zirconium, for corrosion inhibition as well as small concentrations of fission products and corrosion products, a better understanding of the possible interaction phenomena is mandatory. This need stimulated experimental programs at the Brookhaven National Laboratory and elsewhere to determine precisely the liquidus uranium concentration in the bismuth-rich portion of several ternary systems. Early experimental efforts were directed toward an accurate dcmtermination of the U-Bi liquidus over the temperature range from 300' to 800°c. As shown in Fig. 1, the results to date exhibit considerable scatter. The investigations of Bareis,' Teitel,2 Greenwood,3 and Cotterill and hon4 agreed well below 700°c. Greenwood and Teitel extended their studies to higher temperatures but failed to concur in their results. A more recent study by Schweitzer and weekss at Brookhaven National Laboratory between 300' and 725°c, produced values 15 pct lower

Jan 1, 1962

By A. J. Jacobs, J. W. Spretnak, R. Speiser

The activities of nickel in liquid iron-nickel solutions containing from 10 to 90 at. pct Ni were measured over the temperature range .1510° to 1600°C. A special function was devised whereby activities can be computed by a graphical integration using the results of chemical analyses on the vapor phase alone. The liquid solutions studied exhibit negative deviation from Raoult's law, but they approach ideality as the temperature is raised from 1510° to 1600°C. The maximum heat of solution is less than -8.0 kcal per mole. The entropy of solution is less than —2.5 kcal per mole deg at 1510°C, and changes negligibly as the temperature is raised. The liquid iron-nickel solutions do not follow regular solution behavior. THE activities of the components of a liquid alloy system can be determined in favorable cases from the partial pressure of the vapor in equilibrium with the liquid alloy.' Assuming that the vapor over the alloy behaves as an ideal gas, the activity of component i is given by the expression, Where the superscripts 1, v, and o signify the liquid, the vapor, and the pure component, respectively; the f's are the fugacities, and the P's, the pressures. The quantities Pi and Pi can be determined by the

Jan 1, 1960

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

Jan 1, 1950