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By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By M. B. Kahle, A. D. Pernichele

Four types of slope failures in waste dumps are recognized debris flow, foundation failure, edge slump, and blowout. The first three types, although at times causing considerable damage to property and interfering with mine operations, are not usually dangerous to personnel because of their slow rate of movement. The fourth type, the blowout, is the most dangerous because of its explosive mode of failure and lack of forewarning. The December 1969 failure at Verona dump is presented as an example of a blowout. Data from piezometer holes indicate that the blowout was due to perched leach solutions near the face of the dump. The level of water in this zone is very closely related to the rate of leach water application on the dump. A detailed analysis of core samples indicates that the impounded water was perched on a zonal accumulation of jarosite which is associated with a buried dump surface. Drain holes proved successful in controlling perched leach solutions in the critical zone near the face of the dump. Monitoring of the water level in the perched zone is considered essential in preventing blowouts. The use of drain and piezometer holes has allowed an increase in the rate of water application on the dump while preventing additional failure.

Jan 1, 1972

By Nathaniel Herz

PARTING of bullion before shipment to the mint had been considered by the Homestake Mining Co. at various times, but had never been attempted before 1933, be- cause the margin of profit appeared to be too small to warrant the complications in refining. When the gold standard was abandoned by the United States in the spring of 1933, however, parting of the bullion was decided upon. The method selected was the Miller or chlorine process, which consists of the passing of gaseous chlorine into a bath of molten bullion, converting all metals other than gold into chlorides, and remov-

Jan 1, 1935

By Frank G. Snyder, Paul E. Gerdemann

The Southeast Missouri lead district, located about 70 miles south of St. Louis, embraces four important sub-districts and several minor ones. The important sub-districts, in order of discovery, are Mine La Motte, the Old Lead Belt, Indian Creek, and the Viburnum Lead Belt. Descriptions that follow are of geology and ore deposits of the Old Lead Belt. The ore deposits are stratiform in character and are localized in a narrow carbonate bar and algal reef environment on the flanks of exposed Precambrian of the St. Francois Mountains. Ore structures include a variety of primary depositional features such as pinchout zones, disconformities, ridge structures, reefs, and submarine gravity slides. Faulting, prior to and during ore deposition, "prepared" the host rock and strongly fractured areas are mineralized much more intensively and extensively than unfractured parts of the same sedimentary structures. The deposits are epigenetic in character. Mineralization is believed to have occurred at the time that post-lower Ordovician faulting took place. The mineralizing solutions are believed to be concentrated brines from adjacent basins that moved out of the basins during faulting, uplift, and erosion of the St. Francois positive area.

Jan 1, 1968

By W. F. Durfee

In the year 1862 the author of this paper was called upon to design and superintend the erection and working of the machinery of an experimental works for the production of steel by a process

Jan 1, 1884

By Davenport, Edmund S.

THE specific aim of this work has been to study certain forms of internal deterioration which occur in tungsten filaments when subjected to high temperatures under various conditions, and to determine the cause of such deterioration. This would naturally lead to a consideration of methods of control or means of prevention of the phenomena. The deterioration was first noticed as a peculiar condition in the grain boundaries of certain tungsten filaments which had been burned t for long periods in lamps. In these cases it was noted that the grain bound aries contained a number of minute black dots which were at first thought to be non-metallic inclusions. It was demonstrated later that these dots or pits, as they were designated, could be readily produced by burning filaments in an atmosphere of flowing hydrogen. This method was convenient and adequate for the purpose, and was adopted for most of the work discussed in this paper. The evidence accumulated to date indicates that these pits arc actually small voids between the grains. The purpose of this paper is to, present the information on this interesting subject gathered during a period of about 3 years. As applied to tungsten, the subject appears to be of considerable importance, experience having shown that this pitting is frequently associated with poor performance of filaments in lamps.

Jan 1, 1927

By E. H. Sellards

ON Oct. 9, 1929, a sink formed in the Sour Lake salt dome oil field in Texas, and on Oct. 12 a second smaller sink formed at the north margin of the first. The purpose of this paper is to give such observations as it has been possible to make on the earth movement incident to this subsidence. Sour Lake salt dome is typical of the salt domes of the Gulf Coastal Plain of Texas. Structurally the dome is a plug of salt which rises to within 900 ft. or less of the surface. Above the salt is a cap rock consisting of anhydrite with more or less calcium carbonate. The salt plug, as contoured on the cap rock, is circular in outline with, however, some appreciable irregularities. Overlying the cap rock are relatively uncompacted sediments consisting of sand, clay and gumbo.. At the crest of the dome these deposits are no more than 700 or 800 ft. thick. However, the sides of the dome are steep, and the sediments thicken rapidly away from the crest. The sink formed about 1500 ft. northeast of the crest of the dome where the sediments overlying the cap rock are from 1000 to 1200 ft. thick. The cavity permitting the subsidence was quite certainly either in the cap rock or in the salt below the cap rock, so that the sink was formed by the caving of as much as 1000 or 1200 ft. of earth.

Jan 1, 1930

By Fitterer, G. R.

The impact of the work of Herty "et al" on modern liquid steel technology can only be evaluated by first setting the stage as it existed in 1926. It is important to briefly review not only the steel making process and viewpoints regarding methods of refining, but also to describe the tools which were available for research at the time. One must recall that only 15 years before the beginning of this program, the open hearth production exceeded that of the Bessemer in the United States. Many open hearths were still operating on producer gas (a very inefficient fuel), although some plants were converting to the use of natural gas and very few to oil. Continuous rolling of wide strip started this year. The Faraday Society in England held a World Conference on Physical Chemistry in Steel Making in 1925 and the contributions to this work created considerable interest throughout the world and it appeared that physical chemistry might convert the art of steel making into a science. These papers, however, attempted to solve the problems through the use of the older physical chemical concepts such as Nernst's numbers, etc. and considerable data were missing. In 1923, Lewis and Randall had published their book Thermodynanzicsl and this was later to establish and standardize the steps which are now accepted for the calculation of physico-chemical equations. At the time this research work was started, there were no small high frequency induction furnaces. Northrup had just invented his high frequency furnace and a few large units had been instilled in plants. The vacuum fusion method lor the determination of oxygen in steel was

Jan 1, 1957

By Robert L. Clayton, Arthur Baker

Two massive sulfide zinc-copper ore bodies are in quartz-sericite schist (probably formed by regional metamorphism of sediments) and andesite of the Precambrian Yavapai Series, on opposite sides of a large rhyolite mass. The Copper Queen ore body is conformable with bedding of its schist host rock, but the Old Dick ore body probably crosscuts the strata. A lens of low-grade mineralization in chlorite schist, associated with the Old Dick ore body, crosscuts through 150 feet of strata. The ore bodies are almost entirely enclosed by premineral faults with less than 150 feet of displacement. The minerals of the ores are pyrite, sphalerite, and chalcopyrite, with minor arsenopyrite and galena and small amounts of intimately associated chlorite, sericite, and calcite. Old Dick sphalerite-chalcopyrite intergrowths have mutual boundaries, and sphalerite grains contain abundant exsolved chalcopyrite. Copper Queen sphalerite-chalcopyrite intergrowths have extremely ragged boundaries, the sphalerite contains no exsolved chalcopyrite, and the ore overall has a schistose texture. The pre-mineral fault on the hanging wall of the Copper Queen ore body has had 100 feet of post-mineral displacement. Wall rocks of the Old Dick ore body locally have been sericitized. Andesite and quartz-sericite schists for at least several hundred feet around both ore bodies have been chloritized erratically and contain traces of copper.

Jan 1, 1968

By Hermann Bach, Walther Hänig, Willi Gehrhardt, Ernst Theurich, Walter Langner

With the construction of the Magdeburg zinc works, the Georg von Giesche's Erben Mining Co. of Breslau has to a certain extent completed the program of reconstruction which it set as its goal after the boundaries of Upper Silesia were drawn by the Treaty of Versailles. During its history, covering.more than two centuries, zinc and lead mining has been its chief activity. Through the new boundaries established, it lost to Poland all its mines and smelters, including five distillation smelters. Of its extensive properties, there remained only an apparently unimportant and unexplored portion of the old Bleischarley ore field which, however, happily made possible the resumption of its old business. In 1925 the Deutsch-Bleischarley shaft-only a few kilometers from the old Bleischarley shaft—was sunk and developed, and in May 1926 production of lead and zinc ore was resumed. As facilities for smelting were lacking, the ore was at first delivered to the neighboring smelters, which had now become Polish. Realization of the plan to build its own zinc works had to be postponed at first for lack of capital. In the meantime, however, plans for the new works were worked out in all details. After extensive experimentation in a semicommercial pilot plant it was decided, at the end of 1928 and the beginning of 1929, to use the electrolytic process and, for economic reasons, to place the works at Magdeburg. With zinc at the approximate price level that had ruled since the Deutsch-Bleischarley mine had begun working, it was hoped that the plan could be completed in 1930 with the company's own resources. However, falling metal prices, already noticeable in 1929, made this impossible, and further postponement for a time became necessary. Finally, at the end of July 1933, the funds for building the works became available, in the form of a loan granted under the first employment

Jan 1, 1937

By Alfred Weiss

Over the past 25 years hard-rock mining companies have developed a number of profitable computer applications which appear applicable to operations in the coal industry. The evolution of these applications are described and the most profitable discussed. The basic nature of these systems is that they must cut across organizational boundaries. While technological advances contributed significantly to the successful implementation of computers within mining, the human aspects related to organization, management and control of systems projects remain as key to future success in coal as they were and still are in hard-rock mining.

Jan 1, 1983

By G. C. McLachlan

Two papers dealing with Noranda's milling operations have already been presented. The first1 of these covered the initial metallurgical problems connected with the treatment of the ore, while the second2 described the development of the mill from a 500-ton unit in 1928 to one with a daily capacity of 3000 tons less than six years later. At the time the second paper was written the equipment whirh had been installed to bring the mill capacity up to 3000 tons was being tuned into production and for this reason, though each step had previously been tested by a large-scale pilot operation, it was thought advisable to withhold metallurgical data until any starting-up difficulties had been overcome and anticipated requirements fulfilled. These requirements called for an improvement in gold recovery without any lowering of the previous ratio of concentration, and the pages that follow deal with the methods by which this result was obtained. An idea of the character of Noranda concentrating ore will be gained from an inspection of the following mineralogical analysis of the ore treated by the mill during 1933: MineRal Content Mineral ConteNt Chalcopyrite, per cent..... 6.8 Silica and silicates, per cent............ 18.3 Pyrite, per cent........... 22.1 Gold, native and as telluride, oz. per ton 0.15 Pyrrhotite, per cent....... 51.5 Silver, probably as argentite, oz. per tou 0.35 Magnetite, per cent....... 0.5 Thesr figures, which are typical, show that over 73 per cent of the ore treated consists of pyrite and pyrrhotite. Determirnation of the proportion of unrecovered gold associated with each of these minerals was therefore of primary importance in developing a suitable method for improving gold recovery. As pyrrhotite is magnetic, this information was obtained by making magnetic sorting tests on samples of the mill tailing and screening the material thus segregated. This showed that the magnebtic material finer

Jan 1, 1935

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By E. von Maltitz

IN his highly interesting paper on "Piping and Segregation in Steel Ingots,"1 Prof. Howe emphasizes the effect of successive phases of internal pressure in the ingot in the evolution of gas, and the consequent formation of blow-holes. From his statements in other places, it may be inferred that he does not here intend to ignore the other variable factor, temperature, but rather to discuss this one more particularly. At all events, it is my purpose not to engage in controversy with Prof. Howe, but rather to contribute, towards the complete elucidation of this important subject which we all desire, my own views and experience. If, in doing so, I specially emphasize other factors than pressure, I need not be understood as denying what I do not think it necessary to discuss fully. Nor, in presenting my own original conclusions, need I be understood as claiming to be the first who ever reached or announced them. Many things are asserted or suggested upon inconclusive evidence; and to confirm such tentative propositions may be as valuable a service as to overthrow them. In the following passage, Prof. Howe adduces analogies, based upon the behavior of charcoal and of water, respectively, which seem to me questionable "In general, the. solvent power falls as the pressure falls ; and in general it rises as the temperature falls. Thus, to heat a solid, for instance charcoal, may expel part of its dissolved gas ; and a tumbler of water drawn cold from the faucet gradually evolves gas, as it stands and warms up on the sideboard." (p. 238.) Charcoal is a solid body, which has the property not only of absorbing gases in large quantities, but also of expelling the thus absorbed gases upon heating. A comparison between charcoal and iron as to the absorption of gases is scientifically not possible ; the gas-content of charcoal is partly due to the

Sep 1, 1907

By Herbert Hoover

I HAVE been greatly honored as your unanimous choice for President of this. Institute, with which I have been associated during my entire professional life. It is customary for your new President, on these occasions, to make some observation on matters of general interest from the engineer's standpoint. The profession of engineering in the United States comprises not alone scientific advisers on industry but, in great majority, is comprised of the men in administrative positions. In such positions, they stand midway between capital and labor. The character of your training and experience leads you to exact and quantitative thought. This basis of training in a great group of Americans furnished a wonderful' recruiting ground for service in these last years of tribulation. Many thousands of engineers were called into the army, the navy, and civilian service for the Government. Thousands of high offices were discharged by them with credit to the profession and the nation. We have in. this country, probably, one hundred thousand professional engineers. The events of the past few years have greatly stirred their interest in national problems.' This has taken practical. form in the maintenance of joint committees for discussion of these problems and support to a free advisory bureau in ,Washington. The engineers want nothing for themselves from Congress.. They want efficiency in government, and you contribute to the maintenance of this bureau out of sheer idealism. This organization for consideration of national problems has had many subjects before it, and I propose to touch on some of them this evening.

Jan 1, 1920

Jan 1, 1925

By Salinger, Herbert

WITH the large amount of metallurgical re- search work now being done and the constant effort of the engineer to effect economies of operation, I think it is a safe prediction that the next few years will see a great change in the handling of mine products. The well-managed mine, with sufficient ore reserves to warrant the necessary plants, will increasingly call upon the metallurgist and chemist for the solution of its problems. Shipping sorted ore or concentrate to the nearest smelter will not be the course followed. From ore to metal, or at least to a product directly salable to the consumer, will be the practice followed. As a consequence, mine managers will be increasingly interested in metal trade problems. By metal trade I mean the buying, selling, shipping, handling, and all the practices, forms and customs that go to make up the trade.

Jan 1, 1928

By Louis, Jordan

THIS paper presents in an abbreviated form the chief points of interest in an investigation of the tarnish-resistant qualities of silver alloys, an investigation which has been carried out as a joint research by the Bureau of Mines and the Bureau of Standards and will later be reported in detail in an official publication from these bureaus. In 1923 a Commission of Gold and Silver Inquiry was created by a Resolution of the U. S. Senate to study the causes of the depressed condition of the gold and silver industry. In cooperation with this commission the Bureau of Mines made a preliminary survey to determine in what ways, if any, it might be possible to increase the uses of silver. One of the possibilities indicated by this survey was the development of silver alloys which should be non-tarnishing, or at least less-tarnishing, than the usual sterling silver (copper-silver). The preparation of a rather wide variety of silver alloys and the determination of their behavior under accelerated tarnish tests in the laboratory was therefore undertaken by the Bureau of Mines and Bureau of Standards as a joint investigation.

Jan 1, 1927

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (-=,6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by Pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (=10-6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960