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By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph's Howe Memorial Lecture' gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By M. C. Flemings, T. S. Piwonka

Pore formation is examined analytically in cellu-larly solidified single crystals, in cylindrical castings of pure metals and alloys, and in unidirectionally solidified castings. Effects are considered of fluid flow. dissolved gas, and surface tension. Experimental results show that flow through a partially solid "mushy" aluminum alloy obeys relations similar to those applicable for flow through other types of porous beds. Flow rate is proportional to the square of the fraction liquid (fL) for fL less than 0.3. Results indicate models chosen for mathematical description of pore formation in alloy solidification are valid. ONE of the solidification variables which is influential in determining mechanical properties of castings and of wrought material produced from cast ingots is porosity. This porosity may result from shrinkage, dissolved gases, or a combination of both, and may take the form of either macroscopic pores in localized areas of the casting or microporosity evenly distributed throughout large areas of the casting. In alloys which freeze over a range of temperatures some microporosity is generally found after solidification. There has been much discussion as to whether the micropores are caused primarily by shrinkage, by gas, or by a combination of both.'-3 There has, however, been little experimental or analytical work performed to delineate the relative contributions of shrinkage and gas in causing microporosity or to quantitatively describe the influence of processing variables on microporosity. Porosity other than microporosity (e.g., center line shrinkage) has also received only limited quantitative treatment.495 The aim of this work is to examine analytically the general problem of pore formation in solidification and to perform limited confirmatory experiments. Consideration is first given to shrinkage porosity in pure and nearly pure metals (shrinkage in cellular growth, centerline shrinkage in cylinders). Next, a discussion is given of formation of shrinkage-caused microporosity in unidirectional solidification and in "mushy" solidification. Finally, influences of dissolved gas and surface tension on microporosity are examined. Numerical results are given for aluminum and an aluminum alloy. Typical examples of microporosity are shown in Figs. 1 to 3, for 1) cellularly solidified aluminum, 2) sand-cast aluminum alloy, and 3) low alloy steel. SHRINKAGE POROSITY IN PURE AND NEARLY PURE METALS 1) Cellular Growth. In cellular freezing of an impure liquid, liquid grooves may exist over a considerable length of the growing crystal.6 The cross-sectional area of the grooves decreases with increasing distance from the cell tips; the root of the groove is blunt if the liquid at this point reaches eutectic composition. As a result of volume contraction during solidification, flow occurs down the groove, parallel to the growth direction; hence, there must be a pressure drop from the groove entrance to points within the groove. The geometry of the groove is simplified to that of a circular cylinder of radius r and length L, Fig. 4, L » r, and a simple and useful limiting case is obtained. This is that, in the circular cylinder freezing at constant velocity, the pressure at the root of the groove is lower than that pressure at radius r in grooves of other geometries where r decreases continuously to a lower limit at L. As discussed below, a pore resulting from a given pressure difference

Jan 1, 1967

By C. S. Matthews, G. L. Stegemeier

In one field in South Texas, approximately 72 per cent of the pressure build-up results show a characteris-i.rtic "hump" (i.e., the pressure builds up and then falls off) which makes interpretation by. standard methods impossible Correlation of size and time of hump with formation permeability. well productivitv index, and method of completion led to the tentativc, conclusion that the humps were caused by segregation of gas and oil in the wellbore after closing-in"'. This conclusion was confirmed by performance of simple laboratory bubble-rise experiments, by theoretical bubble-rise time calculations, and by a detailed calculation of PVT behavior in the well of a particular well Oil which accurate Surface and bottom-hole pressure measure-ments were untile. The hump behavior has since been found to occur in many other fields. The cause, however, is not the mine in all cases. In some of these the hump is trace-ahie to leaks in the tnbing which allow influx from the annulus after closing-in. In other cases the hump is traceable to leaks in the device separating pay horizons in dually completed wells. It is concluded that the recording of both surface and bottom-hole pressures is desirable in wells which show an anomalous build-up behavior. A number of field examples is discussed where use of both sets of measurements enables the cause for anomalous behavior to he found, (and a reasonable interpreation of bottom-hole pressure to be made. INTRODUCTION Theoretically the pressure build-up in an infinite reser-voir should be a linear function of In [(t + at)/nere t is the production time and At a the closed-in time. Some of the variations from this behavior arc well known, such as the curved portion immediately after shut-in which results from after-production and skin effect, and the flattened end portion which results from boundary effects in a limited reservoir. The effect of stratified producing zones and irregular geometrical drainage patterns may also contribute unusual characteristics to build-ups. However, the effect of still another phenomenon—that of movement of fluids within the wellbore—has been neglected in most build-up studies to date. Fluid movements within the wellbore after shut-in occur as a result of after-production, packer failures, leaks in the casing or tubing, or buoyancy of the gas phase when both gas and liquid are present in the well. Each of these movements can influence the pressure build-up, sometimes sufficiently to negate use of the data for computing permeability or stabilized build-up pressure. Examples of each of these phenomena are discussed below. FIELD OBSERVATIONS ON HUMP BUILD-UPS In approximately 75 per cent of the wells in a medium-sized field in South Texas the pressure build-up curves rise to 3 maximum and then decline to what appears to be a stabilized reservoir pressure as shown in Fig. I. Similar behavior has also been observed in wells in other fields in Texas and Louisian:,. Because of the possibility of such behavior being a mechanical failure of the pressure bomb. the bombs were run in tanden into one well which had been known to exhibit this behavior. When both bombs recorded identical curves with the characteristic hump, it was inferred that the unusual build-up is a result of well or forma-

By C. S. Land

Relative permeability functions are developed for both two- and three-phase systems with the saturation changes in the imbibition direction. An empirical relation between residual nonwetting-phase saturation after water imbibition and initial nonwetting-phase saturations is found from published data. From this empirical relation, expressions are obtained for trapped and mobile nonwetting-phase saturations which are used in connection with established theory relating relative permeability to pore-size distribution. The resulting equations yield relative permeability as a function of saturation having characteristics believed to be representative of real systems. The relative permeability of water - wet rocks for both two- and three - phase systems, with the saturation change in the imbibition direction, may be obtained by this method after properly selecting two rock properties: the residual nonwetting-phase saturation after the complete imbibition cycle, and the capillary pressure curve. INTRODUCTION Relative permeability is a function of saturation history as well as of saturation. This fact was first pointed out for two-phase flow by Geffen et al. 1 and by Osaba et a1.2 Hysteresis in the relative permeability-saturation relation also has been reported for three-phase systems.3 Since saturations may change simultaneously in two directions in a three-phase system, four possible relationships arise between relative permeability and saturation for a water-wet system. The four saturation histories of this system were given by snel14 as 11, ID, DI and DD. I and D refer to the direction of saturation change (imbibition and drainage), with the first letter of the symbol indicating the direction of change of the water phase. As used in this paper, the second letter of the symbol refers to the direction of saturation change of the gas phase, i.e., D and I indicate an increase and decrease, respectively, in gas saturation. Only a few three-phase relative permeability curves have been published. Leverett and Lewis5 published three-phase curves for unconsolidated sand, and Snell4 reported results of several English authors for both drairrage and imbibition three-phase relative permeability of unconsolidated sands. Three-phase relative permeability curves for a consolidated sand were published by Caudle et a1.3 for increasing water and gas saturations (ID). Corey et a1.6 reported drainage (DD) three-phase relative permeability for consolidated sands. Recently, Donaldson and Dean7 and Sarem8 calculated three-phase relative permeability curves from displacement data on consolidated sands, also for saturation changes in the drainage direction. The only published three-phase relative permeability curves for consolidated sands with saturation changes in the imbibition direction (11) are those of Naar and Wygal.9 These curves are based on a theoretical study of the model of Wyllie and Gardner 10 as modified by Naar and Henderson.11 Interest in three-phase relative permeability has increased recently due to the introduction of new recovery methods and refinements in calculation procedures brought about by the use of large-scale digital computers. The scarcity of empirical relations for three-phase flow, and the experimental difficulty encountered in obtaining such data, have made the theoretical approach to this problem attractive. RELATIVE PERMEABILITY AS A FUNCTION OF PORE-SIZE DISTRIBUTION Purcell used pore sizes obtained from mercury-injection capillary pressure data to calculate the permeability of porous solids.12 Burdine extended the theory by developing a relative permeability-pore size distribution relation containing the correct tortuosity term.13 The works of Purcell and Burdine were combined by Corey14 into a form that has

Jan 1, 1969

By E. T. Turkdogan, L. S. Darken

Using the quadratic formalism, thermodynamic equations are derived for the composition dependence of the heat and entropy of mixing. The applicability of these equations is confirmed by available experimental data on the activities and heats of mixing for binary metallic systems of Group ZZB elements. In a recent paper arkeen' introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. That is, in the terminal region, which may extend to as much as 60 at. pct, the logarithm of the activity coefficient, log y,, of component 2 is a linear function of (1 - N,)' where N2 is the atom fraction of component 2. Similarly, for the other component, log yl is a linear function of (1 - N,)'. A number of iron-base binary liquid alloys were shown to obey this quadratic formalism. arkeen' extended this formalism also to any corner of a ternary system and showed that the activity coefficients of the components 1, 2 and 3 (1 is taken as the solvent) can be represented by quadratic terms involving five parameters, four of the binaries and one for the ternary system. Numerous examples given by arkeen' demonstrated the general applicability of the quadratic formalism to iron-base systems over a wide composition range. In this paper further examples are given of binary liquid systems (Group IIB elements, Zn, Cd, and Hg) and of several solid solutions, again demonstrating the appropriateness of this concept. A further purpose of this paper is to extend the quadratic formalism to the enthalpy and excess entropy of binary metallic solutions and to test the equations so found using available experimental data. QUADRATIC FORMALISM FOR HEATS AND ENTROPIES OF MIXING OF BINARY METALLIC SOLUTIONS The following equations, reproduced from Darken's paper, are for the two terminal regions of binary systems. at infinite dilution and a's are temperature dependent parameters to be determined from the experimental data. Although the quadratic formalism is an assumed representation of the data, Eqs. [I] to [4] are thermo-dynamically consistent with the Gibbs-Duhem relation and satisfy Raoult's and Henry's laws as limiting cases. As pointed out previously,' the following form of the Gibbs-Duhem equation facilitates the integration in general but particularly in regions I and 11, where each of the derivatives is constant. The partial molar enthalpy of solution i, (and i; the value of i, at infinite dilution) are related to the activity coefficients y, and y," by the thermodynamic relation Differentiating Eq. [l ] with respect to 1/T and substituting the above thermodynamic relation gives for region (I) It is reasonable to assume that over a temperature range of experimental interest, the enthalpy of mixing is essentially independent of temperature, implying from Eq. [7] that the derivative da,,/d(l/) is also independent of temperature. On the basis of this argument, the temperature dependence of a has the form where £ and S have the units of enthalpy and entropy respectively; they are characteristic parameters for a terminal region of a binary system, e.g. for region (I), C12, S12 and for region (II), d:,,, S2,. Using this equation gives for dff ,/ d(l/), From Eqs. [7] and [9] an expre_ssion is obtained for the composition dependence of L,. Similar calculations are made for El and the results are summarized below for the two terminal regions. For region (I), The corresponding expressions for the molar heat of solution, AHM, are readily obtained from the above equations for the two terminal regions: For region (I),

Jan 1, 1969

By G. Thodos, R. J. Smialek

A method has been developed that permits the correlations of Mehra and Thodos8 and Dastur and thodos2 for binary systems to be used for the prediction of the vapor-liquid equilibrium constants of the light and heavy constituents, Kland Kh, of a ternary hydrocarbon mixture. Furthermore, the unique relationship observed in this study, i.e., a plot of log Ke/Ki vs log Kp/K h is linear and passes through the origin, permits the calculation of the K-value for the intermediate component. This approach has been used to establish K-values for the constituents of the three ternary hydrocarbon systems used to develop this method and has also been applied to two additional ternary hydrocarbon systems to yield an average deviation of 7.7 per cent resulting from a total of 294 points for the five ternary systems considered. INTRODUCTION The rigorous calculation of vapor-liquid equilibrium constants for systems containing two or more components is a difficult problem and becomes extremely complex at elevated pressures and for conditions approaching the critical point. Although thermodynamic relationships can be developed to account for the vapor-liquid equilibrium behavior of simple systems, their use is limited because the necessary PVT data for these systems are not generally available. To establish a method for calculating K constants directly, without any recourse to the PVT behavior of a system, Mehra and Thodos8 applied the principle of corresponding states to the vapor-liquid equilibrium constants of binary hydrocarbon systems. They developed a series of charts which made possible the prediction of K-values for all binary hydrocarbon systems not containing methane. This work has been extended by Dastur and Thodos2 to include binary hydrocarbon systems containing methane. The charts developed in these two studies cover the high-pressure region and are applicable to conditions in the vicinity of the critical point. The ability of this approach to predict vapor-liquid equilibrium constants of binary hydrocarbon systems suggests that this method may be extended to the prediction of the K-values of the components of ternary hydrocarbon systems. In this investigation, the charts developed for both the methane and non - methane binary systems,2,8 together with mixture rules developed in this study, have been used to predict the K-values of the light and heavy components of a ternary hydrocarbon system. These calculated values are then used to establish the K-value of the intermediate component through the use of a novel relationship developed in the present study. DEVELOPMENT OF METHOD FOR PREDICTING K-VALUES OF TERNARY SYSTEMS The application of the corresponding state charts developed for binary hydrocarbon systems is restricted to those systems containing two components. The extension of these correlations to three-component systems requires that the ternary system be reduced to an equivalent binary, which can be treated in a manner consistent with the corresponding state development. To establish such an approach, the vapor-liquid equilibrium constant of the light component K is first calculated by assuming that the ternary mixture consists of the light component and a pseudo-heavy component of the intermediate and heavy constituents of the original ternary. To establish the vapor-liquid equilibrium constant of the heavy component Kh, the light and intermediate constituents of the ternary are combined to form a pseudo-light component of another equivalent binary system. The calculated values Kl and Kb are then utilized to calculate the vapor-liquid equilibrium constant of the intermediate component EQUILIBRIUM CONSTANT FOR LIGHT COMPONENT K To calculate the K value of the light (most

Jan 1, 1965

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10' cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;' the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson's equation is

Jan 1, 1965

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc.* When Mr. Carnegie made his gift which made possible a home for the engineering societies, a separate corporation was organized to act as a holding company and to manage the common property. This was long known as the United Engineering Society but the name has now been changed to one which more nearly reflects the real function of the corporation. It holds title to the Engineering societies Building and to various funds placed in its charge and is managed by a Board of Trustees of which three are chosen by each of the four societies, American Institute of Mining and Metallurgical Engineers, American Society of Mechanical Engineers, American Institute of Electrical Engineers and American Society of Civil Engineers, which own equal and undivided interests in the property. The land and building cost two million dollars. The interest of each of the Founders societies, aside from especial trust funds, is now valued at $493,352. The A. I. M. E. trustees are Arthur S. Dwight, J. V. N. Dorr and H. A. Guess. George D. Barron will succeed Mr. Guess as trustee at the end of this year. The President of the Board is Francis Lee Stuart and the Secretary, Alfred D. Flinn. The Engineering Foundation The Engnieering Foundation was established in 1814 as a result of a gift of $200,000 made by Ambrose Swasey. It is intended not only "for the Furtherance of research" along broad lines but also "for the advancement of" a wide variety of other activities of benefit to engineering as need arises. The endowment fund, which now amounts to $630,000, is administered by the United Engineering Trustees, Inc. Through The Engineering Foundation board, on which the Institute is now represented by J. V. N. Dorr, John M. Callow and Galen H. Clevenger, the income of the endowment, approximately $28,000 a year, and funds contributed for special projects are appropriated for the purposes intended. H. C. Bellinger will succeed Mr. Callow on the board at the end of this year. Alfred D. Flinn is Secretary- and Director. Researches of wide interest in many lines have been aided by Engineering Foundation. . A grant from it to the Mining Methods Committee assisted in the preparation of Volume 72 of the Transactions. For several years the Foundation has aided in support of the study of Blast-furnacc Slags by R. 8. McCaffery at the University of Wisconsin, sponsored by the Institute. The Foundation has raised over $230,000 to support the Alloys of Iron Research endorsed by the Institute and George B. Water-house is serving as Chairman and Director of the Iron Alloys Committee which has been brought together to direct this work. The Foundation has also on recommendation of the Institute made a grant in aid of the studies of Mining and Strata being conducted at Columbia University by P. B. Bucky, which promise information of great usefulness relative to mine subsidence and support of ground. John Fritz Medal Board of Award The medal was established in 1902 and lias since, been awarded not oftener than annually by a hoard of sixteen members, four representatives each from the American Societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers.

Jan 1, 1930

By N. K. Chen, C. H. Mathewson

Single crystals of high purity aluminum of various orientations were carefully documented after plastic extension. Special attention was given to the formation of slip lines, deformation bands, and asterism. An explanation for the geometry and mechanism of formation of deformation bands is considered. WHILE the general process of plastic extension of face-centered cubic metals is well understood,' the accompanying structural changes due to slip and rotation are far more complex than ordinarily assumed. In the case of stretched single crystals of aluminum, the complicated behavior is especially marked by the formation of deformation bands, as first indicated by Collins and Mathewson." Such bands were believed by them and also by others,".'7 who have discussed banded structure in general, to represent one of the important modes of lattice reorientation and to be intimately connected with the recrystallization process. Yet, despite their fundamental importance to the understanding of the mechanism df both plastic deformation and recrystallization, practically no study of the crystallographic features of these bands in their relationship to the conventional slip process has been attempted. This paper describes part of an extensive investigation on the structural behavior during plastic deformation of aluminum single crystals and is especially concerned with the characteristics of deformation bands. The investigation of the subsequent re-crystallization of deformed aluminum single crystals will be discussed in a later publication. Experimental Procedure Single crystal specimens of 99.996+ pct pure aluminum, Yz in. in diam and 5 to 6 in. in length were made both by the Bridgman method5 nd by a modified temperature gradient method.'* Crystals were selected in which the lineage deviation did not exceed 2"; i.e., as determined from the back-reflection Laue X-ray photograms. These crystals were radiographed to insure that no internal porosity was present. The orientations showed good coverage of the whole area of the Taylor and Elam triangle.' Orientations of the crystals were obtained by the back-reflection Laue technique described by Greninger." Crystals so selected were tapered very carefully in a lathe to obtain a linear decrease in diameter from 0.500 to 0.350 in. along a gage length of 3 in. This is considered desirable because it permits a strain gradient to be introduced in a single specimen at one initial orientation. The advantages of tapered crystals for studying the development of slip lines and recrystallized grains have been pointed out by previous investigators." The cold-worked layer resulting from the machining operation was removed by alternate etching in aqua regia and careful polishing with 2/0 emery paper until undistorted Laue back-reflection spots were obtained. A homogenization treatment at 600 °C for 24 hr was then introduced to insure the removal of residual stress. Two of the crystals so prepared were also checked by use of a glancing angle technique. Using a copper target, at 30 kv and 10 microamperes, a monochromatic beam was positioned at right angles to the axis of the crystal about which it rotated. The time of exposure was 24 hr. From these X-ray photograms, it was concluded that the present method of preparation of single crystals is satisfactory. Following this procedure, the crystals were elec-trolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. Intermittent

Jan 1, 1952

By M. D. Hassialis

[Surface Areas of Concentrates and Collector Coatings (T.P. 2002, by A. M. GAUDIN and G. S. PRELLER, Min. Tech., May. Discussion by M. D. HASSIALIS and the authors) . I Activation of Minerals and Adsorption of Collectors (T.P. 2082 by J. ROGERS and K. 1'. SUTHERLAND, Min. Tech., Nov. Discussion by A. F. TAGGART and the authors). . . . 3 Correlation between Mineral Behavior in Cataphoresis and in Flotation (T.P. 2005 by A. If. GAUDIN and S. C. SUN, Min. Tech., May. Discussion by M. D. HASSIALIS). . . . . . 8] Surface Areas of Concentrates and Collector Coatings M. D. HASSIALIS.*-In the current flotation theories there exists a common gap spanned by a common assumption pertaining to the arrangement and orientation of the collector ions at the solid surface. Also common is the belief that contact angle and flotation performance are dependent upon the arrangement and orientation of collector ions. This stimulating and informative paper sheds some light upon this general problem. One of the indices of arrangement is the area available per collector ion; in this connection, Gaudin and Preller have applied the B.E.T. method for surface determinations. In a surprising number of cases, their results show a greater specific surface for tailing than for concentrate. This cannot be accounted for by the differences in specific gravity and is attributed to the presence of clay minerals of "primary" sluices in the tailing. This is not a satisfactory explanation, for experience shows that when free slimed clay minerals are present in a flotation cell they will be carried mechanically into the concentrate. A part of the answer to the decreased specific surface of the concentrate would appear to be its usual flocculated condition, yet this should not entirely account for the large spreads reported. The possibility occurs that the nitrogen adsorption isotherms for clean mineral and collector-coated mineral are different. If that were true, and if the coated mineral surface exhibited decreased adsorptive powers, the discrepancy might vanish. In discussing the disposition of collector ions at mineral surfaces, the authors adopt the more consistent viewpoint that there exists some agreement between the ions of the substrate and those of the superstrate. In the case of xanthate ions on galena, a possible arrangement is shown in Fig. 2. This arrangement shows every xanthate ion being shared by two lead ions, whereas the chemical composition calls for two xanthate ions for each lead ion (p. g). This whole discussion is misleading. In the first place, it is known that xanthate ions are not abstracted by unoxidized galena, hence Fig. 2 should show as the substrate not Pbs but PbS„ Om. It would be equally erroneous to use the lattice arrangement of PGSO4, since the surface properties of xanthate-conditioned anglesite differ from those of xanthated galena. It is highly probable that the state of the galena surface exploited in its flotation is ephemeral, since weathered galena is only poorly, if at all, collected by xanthate. Just how a substrate of oxidized galena is to be pictured depends upon one's conception of the transformation from galena to anglesite. This writer is inclined to the following sequence of events. Surface sulphide ions undergo progressive oxidation. As more oxygen is taken up by the sulphide ions they become displaced from their equilibrium positions in the galena lattice, thus accommodating for the larger volume of the S„ Om ions. Concomittant with this change the forces acting on the lead ions

Jan 1, 1946

By M. H. Pilkuhn, H. Rupprecht

The junction luminescence of GaAsxP1-x diodes containing up to 47 pct Gap was studied. Diodes were prepared by diffusing zinc into n-type material which was eithw boat- or vapor-gvown. Observations concerning the energy and the line shape of the spontaneous emission are presented and discussed; in particular the influence of inhomogeneous phosphorus distribution is considered. The role of reabsorption of the junction radiation is pointed out. With increasing current, the peak emission shifts to higher enwgy. This is alm true in cases where slow line narrowing occurs simultaneously. The length dependence of the threshold current density for lasing at 77 °K was examined for lasers made from the same material. It was found that longer lasers have lower threshold curvent densities, Estimates of the characteristic laser losses are given. Data concwning the range of Gap concentration in which stimulated emission was observed are presented. FORWARD-BIASED p-n junctions in mixed alloys of GaAsxPl-, emit light whose wave length depenfs on the composition of the alloy ranging from 8400A (x = 1) to 5350A (x = 0) at 77°K. Laser action in vapor-grown material was first reported by Holonyak and evacqua,' and in boat-grown material by Ainslie, Pilkuhn, and Rupprecht.' In both cases this was observed for low Gap concentration where GaAs,Pl-, is still a "direct" semiconductor with the lowest conductance-band minimum at k = 0 and a subsidiary minimum in the [loo] direction. As the Gap concentration is increased, the subsidiary [loo] minimum in the conduction band is lowered and finally becomes the lowest minimum for Gap concentrations above 50 pt,3 making the alloy an ''indirect" semiconductor. It is of interest to determine up to which Gap concentration stimulated emission can be observed. EXPERIMENTAL Boat-grown material was prepared by N. Ainslie of IBM by horizontal Bridgman technique. The material was n type and silicon-doped up to a concentration of 10'' cm-'. Vapor-grown material was made by E. Hull of IBM or received from Merck & Co. Diodes were fabricated in a similar manner as in the case of GaAs by zinc diffusion. Details about the diffusion can be found in a later paper.4 All diodes were of Fabry-Perot structure with two parallel sides cleaved and the other two sides sawed. Their width ranged from 50 to 150 p and their length from 50 to 700 p. RESULTS AND DISCUSSION Spectral Distributions. A typical display of the junction luminescence of a GaAsxPl-, diode is shown in Fig. 1. The liquid-nitrogen and room-temperature curves which were taken at a very low current (25 ma dc) show a relatively sharp high-energy emission which is band-edge radiation. They also show a broad low-energy emission which is due to transitions to deep impurity levels. This latter emission line may have different shapes and positions depending on the nature of the material. It can sometimes be quite near the band gap giving rise to "bumps" in the high-energy line. The results presented in this paper will be concerned only with the high-energy emission which becomes more intense relative to the low-energy emission when the current is increased and the temperature is lowered.

Jan 1, 1964

By P. S. Rudman

Crystal-structure occurrences in binary phase diagrams of fifth- and sixth-period elements, zirconium through palladium and hafniun through platinum, are surveyed with the conclusion that average .group number GN is the dominant correlative. This is interpreted in terms of curves of enthalpy differences between competitiue structures that are continuous func -tions of GN. It is further reasoned that the absolute formation energies may also be continuous functions of GN and if so can be simply obtained from the regatives of the heats of sublimation of the elements. It is shown that from such a heat of formation-GN plot the heats of mixing of alloy systems can be quantitatively predicted. For example, for sixth-period alloys very large exothermic heats of mixing are predicted for systems that span GN = 6 (i.e., Hf-Pt, Ta-Os, ...). Thermodynamic data with which to test these predictions do not appear to be available. If in the latter transition (A subgroup) elements we eliminate from consideration the fourth period where magnetic terms contribute to crystal-structure stability, as shown in Table I, there is a very regular sequence of structures. Using the group number (GN) assignments of Table I, which differ from the usual assignments of 8 to the elements listed as 8 through 10, it is perhaps trivial to say that the phase occurrence is a unique function of GN. However, the interesting aspect of alloys from among these elements is that the alloy structures also appear to correlate with GN. The GN for an alloy is given as GN = SixiGNi, where xi and GNi = atomic fraction and GN of component i, respectively. It is difficult to credit anyone in particular with having discovered this correlation, so many people have implicitly or explicitly employed it in the last 10 years. However, Bloom and Grant' in their correlation of s-phase occurrence with total number of d + s electrons were certainly one of the first to appreciate the correlation and Hume -Rothery2 appears to be responsible for the use of average GN as defined above. Only in the last few years have the phase diagrams of enough alloy systems been determined for this correlation to be surveyed with any degree of completeness. We shall here, in an abbreviated format, summarize the available phase-diagram literature and discuss some consequences of the GN correlation. BINARY DIAGRAM SURVEY In Figs. 1 to 3 the phase occurrences are summarized. In Fig. 4 the occurrence limits for the more common structures are summarized. That the GN of an alloy falls within the occurrence limits of a particular structure is a necessary but not a sufficient condition for the appearance of that structure. The preceding figures certainly illustrate that GN is a dominant correlative for structures of these elements. Many of the diagrams have complications, with ordering and other phase changes occurring in intermediate phases, that cannot be clearly accommodated in such a schematic survey and have hence been left out. Such omissions cannot, however, negate the GN correlations discussed here. Relative atomic size is also an important crystal-structure determinant and since atomic size varies quite regularly with GN for these elements it is possible that the apparent GN correlation is basically a size correlation. In Fig. 5 relative size occurrence limits are given for intermediate phases and extended terminal solutions. The relative volume, ?v/(v) - 2(vA - vB)/(vA + uB), has been taken as the measure

Jan 1, 1968

By R. B. Ladoo, C. A. Stokes, R. N. Secord, A. L. Hall

INDUSTRIAL mineral history shows that the entrance of new, nonmetallic minerals into commercial production can be expected to occur from time to time. Latest entrant into the field is wollastonite. Except for one short-lived period in Kern County, Calif., starting in 1933, wollastonite has never before been produced on a commercial scale. But the signs are up for its entrance as an economic factor in the mineral market. Small scale experimental production from a deposit near Willsboro, N. Y., started about 1943. A pilot plant was built in 1949-50 and irregular, small scale, production has continued. In early 1951 Godfrey L. Cabot, Inc. of Boston, world's largest producer of carbon black, took an operational lease on the property to study the deposits and make market surveys. This became Cabot's first venture in the mineral field, when they took over operations and began design of a new mill, expected in production in 1953. Properties The properties and major uses of wollastonite are comparable to New York fibrous talc. It has about the same specific gravity and index of refraction as talc, but is somewhat whiter and softer. The two most important fields of use, paint and ceramics, are the same as for talc. Ground wollastonite has a fiber length as much as 13 to 15 times the diameter. This particular property makes it applicable in the paint field and others. In addition, the length-diameter ratio may be controlled to rather narrow limits by choice of grinding method. Another important commercial property is brightness or whiteness. Wollastonite reads from 92 to 96 pct of MgO on the G.E. brightness meter for a 99 pct -325 mesh grind. Purity and uniformity of product are important. Chemically, the wollastonite now being mined analyzes SiO2 51.76, CaO 47.56, FeO 0.46, MnO 0.04, and H2O 0.09 pct. Theoretically pure wollastonite analyzes SiO2 51.75 and CaO 48.25 pct. This analysis indicates over 98 pct calcium silicate, with only small amounts of contaminating ingredients. That these ingredients are not detrimental to color or brightness is shown by the high brightness value of the fine ground material. [ ] By-product calcium silicate from electric furnace production of phosphoric acid has little physical re-semblance. to this wollastonite, being an off color white, and lacking in fibrous crystalline character. Minerology Wollastonite is a calcium metasilicate, CaSiO3, a white, medium hard, fibrous mineral. In this deposit wollastonite occurs as well crystallized aggregates of bladed crystals intergrown with garnet, and with a few percent of green diopside. The beneficiated product is about 75 pct wollastonite, 15 pct garnet, and 10 pct waste, largely middling. Wollastonite-garnet ore occurs in at least two beds. The main bed, varying in true thickness from 30 to 70 ft, dips into the hill at an average 30° and is enclosed in gneisses. Diamond drilling has proven the orebody to an average depth of 200 ft along 2000 ft of outcrop with adequate tonnage for many years of quarry operation. The wollastonite-garnet ratio varies locally, but average composition is uniform over long distances. A friable ore, it is easy to drill, shoot, and crush. Beneficiation Unlike talc this ore has to be beneficiated. Successful treatment depends upon the fact that it contains virtually nothing but wollastonite, garnet and a minor percentage of diopside. A very pure wollastonite product can be made by high intensity magnetic and/or gravity separation methods.

Jan 1, 1952

By Mark E. Emerson

INTRODUCTION A long time has passed since geologists encountered encouraging mineralization in their regional exploration program for base metals deposits. Detailed drilling during the following two field seasons served to delineate the configuration of the deposit. Various statistical techniques were employed to provide confidence levels regarding the extent of the reserves and to categorize them according to whether proved, indicated or inferred. At this juncture, it appears that the company has an orebody. Time elapsed? - three years; money spent? - $2.5 million. Much remains to be done before the orebody becomes a mine. The company urgently needs to develop new orebodies to replace its existing mines which are being depleted. It therefore has expended sizable amounts in exploration, the life blood of the company. A staff of specialists is maintained to evaluate new projects and to conduct feasibility studies. The scale of new mining projects today is beyond the resources of most mining companies. Bank financing, therefore, is often vital if the company is to survive. The following scenario describes how a company goes about evaluating mine projects and what is needed to meet lender's criteria in securing the needed financing. MINE PLANNING Now that the company engineers have taken over the project, their concern is no longer with finding ore but in developing it. An exploration shaft has been put down and a tunnel driven into the orebody to verify, on a large scale, what has been seen so far only in pencil- like drill cores. A large tonnage bulk sample is mined and shipped off to an independent metallurgical process laboratory for beneficiation testing. The budget is expended to cover engineering studies. Preliminary capical and operating costs are developed in- house and profitability studies are made based or1 assumptions concerning the markets for the main product and the indicated gold, silver, and other by-products. Time elapsed? - four years; cost to date? - $3.5-$4.5 million. The staff prepares its own pre-feasibility study. After review, the Executive Committee authorizes management to proceed with full-scale studies. The task is to make preliminary designs and to develop definitive capital and operating cost estimates. Specialized consultants will be engaged to study slope stability for the open pit and rock strength if underground recovery proves more feasible. If it is near the sea, an oceanographic report might be commissioned to see if the tailings can be disposed of off shore. Environmental impact studies are commissioned from a firm familiar with government requirements and regulations in this important area. The company subscribes for an expensive multi-client study of the supply- demand-price outlook for the product to support its own long-range price forecast. Now all the numbers are available to make a definitive appraisal of the value of the project. Cash flow analyses and sensitivity studies follow. Reams of computer printouts are generated. Time elapsed: five years. Amount spent? - up to $9 million, depending on the size, complexity and attractiveness of the project. Marginal projects always take longer. Finally, an engineering and construction (E&C) company is given the task of integrating and compiling all the data into a feasibility study. The results of dozens of reports, memoranda, computer printouts, and charts are boiled down to one final summary report of a few hundred pages together with conclusions and recommendations. After thoughtful review at a board meeting, the directors authorize management to proceed with detailed engineering work - provided that

Jan 1, 1985

By F. W. Bloecher

DETERMINATION of the surface area of finely divided minerals is of interest to mineral engineers engaged in flotation, comminution, and de-watering studies. In the industrial minerals field, many materials are classified as to fineness according to their specific surface (surface area per unit weight). A method of surface area determination has been tested and used in the Richards Mineral Engineering Laboratories at M.I.T. It involves low temperature krypton adsorption measurements using the technique described by Beebe.' During the past fifteen years a number of new surface measurement techniques have been developed. Those that are broadly applicable to materials dealt with by mineral engineers include the permeability method in which a gas or liquid is passed through the sample, and the low temperature gas adsorption methods first described by Brunauer, Emmett, and Teller."" Efforts to make surface determinations from size distribution curves have long been attempted"."." but because of the uncertainty of sub-sieve size distribution and inaccuracies in screen analyses, the method is at best only a rough approximation. The most widely used gas adsorption method utilizes nitrogen gas." Nitrogen adsorption, however, is not particularly suited as a tool for most mineral engineers because the method is not applicable for surface determinations on coarse materials, that is, materials coarser than approximately 150 to 200-mesh. Other gases have been used in mineral engineering studies, particularly ethane."' lo The use of ethane gas, however, involves .a technique that is too sensitive for most mineral engineering work. The permeability method of surface area determination has the disadvantage of not being sensitive enough to detect the surface represented by minute cracks, the so-called internal surface of a particle. The low temperature krypton adsorption method described by Beebe1 utilizes apparatus and techniques that are essentially the same as those used in the ethane adsorption method."1° The surface area is calculated by the B.E.T. method."-' The krypton adsorption technique is particularly suited to the needs of the mineral engineer because: (1) The method can be used for making surface area measurements of rather coarse materials (35 to 48-mesh), as well as extremely fine materials, such as clays or colloidal slimes with specific surface that might be as high as 20 to 30 mb er g. (2) The use of krypton gas offers the advantage of low saturation pressures (2-3 mm) at the conveniently obtained liquid nitrogen temperature. Therefore the krypton vacuum system need not be designed to measure or withstand internal gas, pressures above one atmosphere as is the case with the nitrogen gas method. (3) The krypton technique offers the safety feature of employing liquid nitrogen, as contrasted to the ethane technique in which liquid oxygen is required. Furthermore, ethane vapor pressure at liquid oxygen temperatures is low (about 10 microns), and a high sensitivity McLeod gage is required for pressure readings. (4) The measurement technique with krypton gas is much simpler and faster, and the apparatus is less elaborate than that required with either nitrogen or ethane gases. Apparatus A krypton surface measurement apparatus like that used at M.I.T. is shown in Fig. 1. It is constructed of pyrex glass. A vacuum is maintained by two mercury diffusion pumps in series backed by a mechanical vacuum pump."' The vacuum thermocouple gage is used for checking the vacuum within the system. This type of gage is quite sensitive down to a pressure of 1 micron of mercury," but may be used to indicate pressures much lower than that

Jan 1, 1952

The work of the Committee on Industrial Preparedness* is well summed up in the following letter written by Thomas A. Edison, Chair-man of the Naval Consulting Board, after President Wilson and signed the army appropriation and army reorganization bills: "The Committee on Industrial Preparedness of the Naval Consulting Board, of which committee Howard E. Coffin is chairman, after a five months' campaign in many ways unique in vigor and vision has played a very definite part in the measures for the national defense which have just become law. It is responsible for having laid the foundation for a true industrial preparedness in this nation. "Five months ago the committee, wholly non-partisan in make-up, acting with the civil, mechanical, mining and electrical engineers and the chemists of the country, members of five great scientific bodies, began its work in' every nook and cranny of the land. The purpose was to prepare American industry efficiently to support the armed forces of America in the event of war. "The public, the business men and the legislators at Washington knew little regarding the demands on industry in connection with modern war. No department at Washington was charged with the duty of coordinating the needs of the army and navy with transportation, industry, and kindred functions. The purchasing, quartermaster's and ordnance departments of the army and navy were unable to buy military supplies except by competitive offering in the open market. No one had considered the need, and no legislative machinery was in existence, for preventing the presence of skilled workers on the fighting front when they would in time of war be needed in the factories, mills and mines of the country. Neither at Washington or elsewhere was there even a list of the industrial resources of the nation in such shape as could be used for practical purposes in case war should come. "The three things, then, that the committee headed by Mr. Coffin set out to do and that now have been brought about were as follows: First, to mobilize concretely the business men of America and their output against a day of need. This meant chiefly to discover in fullest detail just what equipment our manufacturers possessed that might be swung over to supply the army and navy swiftly and bountifully from the hour the colors were raised. In a few weeks this initial task, which has been a truly colossal one, will be at an end. A complete report of the equipment of practically every concern of substantial size in the country is now in the hands of the - committee. Directly in charge of the great inventory has been W. S. Gifford, Supervising Director of the Committee. The second step was to procure legislation making possible the placing by the war and navy departments of annual orders for munitions in small quantities to American manufacturers now not producing such things, so that quietly, efficiently and thoroughly they could learn in time of peace how to supply the government in time of war. The new laws make all this possible. It should be said here that this practice will bring about a geographical diffusion of munition plants all over our country, instead of affording us only a few such concerns for the most part near the exposed seaboards, as at present. It is obvious that this system will also throttle all talk of a munitions trust.

Jan 10, 1916

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968

By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957