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By W. G. Pfann

Under certain conditions, a molten zone can be made to move through a solid by impressing a stationary temperature gradient across the solid. This phenomenon can be utilized in fabricating semiconductive devices, growing single crystals, joining, boring fine holes in solids, measuring diffusivities in liquids, small scale alloying, and purification. Fundamentals and exemplary applications are outlined. ANEW aspect of the travel of a molten zone through a solid is considered in this paper. Whereas, in previously described zone melting techniques,'-' zones were usually caused to move by changing the position or temperature of a heat source, in the present technique a zone is made to move by impressing a temperature gradient across it. For example, a thin layer of molten A1-Si alloy, sandwiched between two silicon slabs having a temperature gradient normal to the layer, will travel through the hotter slab. One feature of temperature gradient zone melting, as this technique will be called here, is that zones of unusually small dimensions can be maintained. This leads to such diverse uses as have been listed in the abstract. In this paper fundamentals of the movement of a molten zone in a temperature gradient, and some practical applications thereof, are outlined. Assumptions The movement of a molten zone through a solid body of solvent substance in which a temperature gradient exists will be discussed. The length of the zone will be its dimension in the direction of motion. The direction of the temperature gradient will be toward the region of higher temperature. To be considered is a binary or higher order solute-solvent system in which the concentration of solute in the molten zone is sufficient to produce a lowering of the freezing temperature of the solvent which is at least of the order of the temperature range impressed on the charge. While we discuss primarily molten zones in a solid matrix, the principles are applicable to solid or vaporous zones in a solid matrix, a requirement being that the diffusivity in the zone be substantially greater than in the matrix. Diffusion of solute into the surrounding solid will be assumed negligible. In general, its presence will not basically alter the conclusions to be drawn. For illustration, a system represented by the partial constitutional diagram of Fig. la will be discussed, in which k, the distribution coefficient defined in the figure, is constant and less than unity. However, the technique is applicable to any solute- solvent system in which one component lowers the melting point of another component. Movement of a Molten Zone in a Temperature Gradient Consider, in the system AB of Fig. 1, where B is designated the solute and A the solvent, the effect of sandwiching a thin layer of solid B between blocks of solid A and placing the whole in a temperature gradient such that the temperature of the layer is above the lowest melting temperature of the system. Surrounded by an excess of A, the layer will dissolve A, becoming molten, and expand in length." As so- lution of A continues, at both interfaces, the mean solute concentration in the zone will move to the right in Fig. la, until at temperature T, the liquid at the cooler interface reaches the liquidus concentration C,. Solution of A thereupon ceases because the liquid T1 is saturated with A. The liquid at the hotter end of the zone, being at temperature T2, is not saturated with A at concentration C1. Hence solution of A continues there and concentration C2 is approached. A concentration gradient therefore is set up in the zone, causing A to diffuse toward the cool end and B toward the hot end. As a result, the liquid at the cool interface becomes supersaturated and a layer of crystalline A containing concentration kc, of B in solid solution freezes. Since a source of A

Jan 1, 1956

By John Hays, Hammond

IT is both a pleasure and an honor to be a guest of the Institute and I thank you, Mr. President and fellow-members, for giving. me the opportunity of meeting you this evening. My esteemed friend, President Smith, has requested me to do a bit of "reminiscing" as to the earlier years of my career as a mining engineer, which has now covered a period of fifty years. Let me reassure you by promising that my narrative will not include all the experiences I have had over that long period. You will, I trust, pardon what might seem egotistical but I do not see how a personal narrative could well be otherwise.

Jan 1, 1928

By K. Adam

Grinding in steel mills adversely affects the flotation of pyrrhotite. The electrochemical nature of inter action between pyrrhotite and active metals was investigated by contacting pyrrhotite with platinum at different applied potentials. Flotation tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were wed to examine the surface properties of pyrrhotite. The formation of hydroxide or oxide and sulfate species of iron through the oxygen reduction reaction at the cathodically polarized surface of pyrrhotite was shown to be the mechanism responsible for the reduced floatability of pyrrhotite.

Jan 1, 1985

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By Grover R. Castle

INTRODUCTION "Project Financing" or "Project Loans" have become increasingly popular in recent years, and commercial banks are being asked to consider more and more of such financing. However, the analysis of this type of loan is quite different from the analysis of a loan to a financially sound corporation based on the company's balance sheet. For this reason Chemical Bank did a study of project loans in an attempt to be more sophisticated in our approach to them. As part of this study, we examined 29 project financings for which information was available. In this article I shall describe project loans and set forth the guidelines we developed, as an aid to credit officers who might have occasion to analyse this type of financing. DEFINITION OF "PROJECT FINANCING" OR "PROJECT LOAN" The terms "project financing" and "project loan" commonly describe the various methods that banks and institutional lenders use to finance the construction of new projects on a basis whereby payout is anticipated from the revenue stream generated by the project. A project financing often involves a loan to a new entity formed specifically to own the project. The analysis of a project loan proposal is quite different from the analysis of other term-loan proposals since it involves a credit decision based on the review of a projection or forecast rather than of historical earnings and/or it involves the reliance on contractual obligations of third parties. Lenders are asked to assume the added risks associated with project loans because: 1. Project financing may permit a company to obtain additional leverage. It is possible for companies to arrange financing on a project basis that could not be arranged as a direct borrowing. For example, a company may not be permitted to borrow more money directly, due to a limitation in a bond indenture. However, a project financing can sometimes be negotiated on a basis not prohibited by the indenture. 2. Often the sponsors of, or the stockholders in, the project are seeking an off-balance-sheet financing. For example, 11 of the 29 projects in our study were arranged on an off-balance-sheet basis and one showed on the balance sheet as a deferred income item. An off-balance-sheet financing, for the purpose of this article, is a financing which does not show as a direct liability on the balance sheet of the sponsors of or stockholders in a project. 3. Projects are often located in a foreign country. The financing is arranged so that the lenders assume the political risk on the loan because many companies rightly believe that this arrangement affords a degree of insulation from political risk not otherwise obtainable. 4. Many projects are jointly owned by several sponsors. This form of financing lends itself well to a situation where a new entity is formed to own a project and do the borrowing. Project loans can be used to finance a variety of activities including development of iron-ore deposits and associated pelletizing plants; development of coal reserves; construction of pipelines, alumina plants, fertilizer plants and refineries; etc. The specific areas of analysis can be quite different, depending upon the type of project being financed. It is important, therefore, to classify the proposal according to the type of project, and also by the nature of the financing - nonrecourse financing, financing covered by a guarantee of completion and financing supported by an undertaking lasting for the life of the financing. I will discuss each of these types in more detail later, but first, I should like to make some

Jan 1, 1985

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10' to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969

By J. A. Norden

MUCH has been written concerning the hoisting equipment of various mines -throughout the country, but most of the literature on the subject, if not all, describes equipment of extraordinary capacity and the small and medium-sized outfits have been neglected. The hoisting equipment here described is capable 'of handling about 1200 tons per day. It has not been worked, to capacity, but 600 to 700 tons, together with men and materials, have been handled in two shifts without any great effort. Only one shaft extends from the surface to the lowest levels of the mine; see Fig. 1. It is composed of three compartments, two of which are used for hoisting and the third for water, air, and electrical lines, and for sinking purposes. In 1909, this shaft was raised from the 1000-ft. (304-m.) level to the 700-ft. There a station was cut and an air hoist installed. At this time all mining operations were confined to the upper levels of the mine; that is; above the 700-ft. The. ore was-dropped to this level through chutes from the 300-, 400-, 500-, and 600-ft. levels and then lowered in cars on cages to the 1000-ft., which is the main haulage adit, the mill and railroad bins being about 3000 ft. from the shaft. Orebodies were, in due time, developed on the 1000-ft. level and below. Therefore, in 1913, the shaft was sunk to the 1150-ft. level and thereafter sinking was continued at regular intervals until the 1500-ft. level was reached. But, hoisting from the 1300-ft. level was a difficult, and slow process with the antiquated air hoist, so, in 1916, it was derided to raise the shaft to the surface and install a modern, electrically operated hoist. This was completed early in 1917 and the hoist was in operation in March of that year.

Jan 8, 1920

By S. Fróes Abreu

The importation of liquid fuels in Brazil amounts to about 1,300,000 tons; 30 per cent of this total being gasoline for automobiles and airplanes. Statistics show an increasing consumption of gasoline notwithstanding the use, daily greater, of fuel alcohol, a domestic fuel of low cost in the producing areas. The Brazilian market for petroleum products has shown a tendency to grow as the country has steadily developed— expansion of the industries in the areas already developed, and also the recent occupation and population of new zones. The war has brought many difficulties to Brazil. It has limited the importation of petroleum products, which came mostly from the United States, Venezuela and Mexico. During the first days of the present crisis automobile and truck traffic was vastly curtailed; but the national activity in the production of more fuel alcohol, and principally in the development of producer gas, has done much to provide a solution for the transportation crisis threatened at the beginning of the gasoline shortage. Many thousands of cars and trucks in Brazil are now burning producer gas made from charcoal. Producer gas for automobiles has been improved by Brazilian engineers and many new types have appeared. - Production There is only one producing oil field in Brazil—the one in the State of Baia, near the Baia de Todos os Santos. The first producing oil well was drilled in Lobato in 1939 by the Federal Government following studies carried on in that area by Oscar Cordeiro, S. Froes Abreu, G. Paiva and J. Amarai. The field and laboratory work done by these men was published in 1936 in a paper entitled " ContribuicBes para a Geologiado Petroleo no Reconcavo (Baia)," which indicated the potentialities of the area as an oil producer. After the discovery of the first producing well, the Brazilian Government issued a decree establishing an area, 60 km. in radius, as a National Reservation. This first well was drilled in Lobato. In no other locality in Brazil is any petroleum produced. Although many wells have been drilled in the southern part of Brazil, on the northeastern coast and in the Amazon Basin, they yield nothing. Actual production is below 1000 bbl. daily. The producing area covers Itaparica Island, Candeias and Arath, Joanes Island and Lobato. Since very little geological information was available, especially about subsurface structure, it was necessary to drill several wildcats in order to collect the data essential in the choosing of good locations. The United Geophysical Co. was contracted to perform a geophysical survey to clear up the major problems concerning the oil deposits in the Reconcavo beds. The best wells in Reconcavo are on Itaparica Island, where the daily flow amounts to about zoo bbl.; in other sectors production is considerably lower and most of the wells are pumping. In the Aratfi sector, near an area of very light oil, there is an important gas field, with wells producing about I0,000,000 cu. ft. daily.

Jan 1, 1944

By S. Fróes Abreu

The importation of liquid fuels in Brazil amounts to about 1,300,000 tons; 30 per cent of this total being gasoline for automobiles and airplanes. Statistics show an increasing consumption of gasoline notwithstanding the use, daily greater, of fuel alcohol, a domestic fuel of low cost in the producing areas. The Brazilian market for petroleum products has shown a tendency to grow as the country has steadily developed— expansion of the industries in the areas already developed, and also the recent occupation and population of new zones. The war has brought many difficulties to Brazil. It has limited the importation of petroleum products, which came mostly from the United States, Venezuela and Mexico. During the first days of the present crisis automobile and truck traffic was vastly curtailed; but the national activity in the production of more fuel alcohol, and principally in the development of producer gas, has done much to provide a solution for the transportation crisis threatened at the beginning of the gasoline shortage. Many thousands of cars and trucks in Brazil are now burning producer gas made from charcoal. Producer gas for automobiles has been improved by Brazilian engineers and many new types have appeared. - Production There is only one producing oil field in Brazil—the one in the State of Baia, near the Baia de Todos os Santos. The first producing oil well was drilled in Lobato in 1939 by the Federal Government following studies carried on in that area by Oscar Cordeiro, S. Froes Abreu, G. Paiva and J. Amarai. The field and laboratory work done by these men was published in 1936 in a paper entitled " ContribuicBes para a Geologiado Petroleo no Reconcavo (Baia)," which indicated the potentialities of the area as an oil producer. After the discovery of the first producing well, the Brazilian Government issued a decree establishing an area, 60 km. in radius, as a National Reservation. This first well was drilled in Lobato. In no other locality in Brazil is any petroleum produced. Although many wells have been drilled in the southern part of Brazil, on the northeastern coast and in the Amazon Basin, they yield nothing. Actual production is below 1000 bbl. daily. The producing area covers Itaparica Island, Candeias and Arath, Joanes Island and Lobato. Since very little geological information was available, especially about subsurface structure, it was necessary to drill several wildcats in order to collect the data essential in the choosing of good locations. The United Geophysical Co. was contracted to perform a geophysical survey to clear up the major problems concerning the oil deposits in the Reconcavo beds. The best wells in Reconcavo are on Itaparica Island, where the daily flow amounts to about zoo bbl.; in other sectors production is considerably lower and most of the wells are pumping. In the Aratfi sector, near an area of very light oil, there is an important gas field, with wells producing about I0,000,000 cu. ft. daily.

Jan 1, 1944

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By Wllliam D. Davis

C OMMERCIAL production of oil in northeastern Oklahoma began in 1897 and in the next two decades this area became one of the greatest oil districts of the time. Its importance is now secondary, but thousands of wells in this area have produced uninterruptedly for more than thirty years. They are now classified as stripper wells. By means of what is known as water flooding their L. production can be considerably in- creased. This practice consists in injecting water under pressure into the sand surrounding an oil well, thus displacing the oil in the pores of the sand and forcing it into the oil well.

Jan 1, 1940

By Chester O. Ensign

Results of the application of geologic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphically controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore.

Jan 4, 1964

By B. D. Saklatwalla

FOR the proper understanding of the inclusion of certain elements in this review it seems necessary to state the meaning of "rare metals." Certain elements occur in deposits limited in extent or concentration, so that the extraction of the element in relation to market conditions becomes uneconomical. Others may occur in extensive and rich deposits but the reduction of the metal may be difficult and costly. Both these conditions effect the same result, namely, make the metal rare and costly. As an example of the first kind may be mentioned radium and of the second, calcium.

Jan 1, 1939

By H. Rees

This paper supplements and brings up to date a report prepared earlier this year and presented at the Eleventh Pan American Railway Congress in Mexico City. Most of the original report is contained in this paper in order to acquaint the reader with the project background. On December 1, 1961, construction of this locomotive was completed. Stationary testing started immediately, and a host of problems in various areas were uncovered. Many of these had no relation to the use of coal in a direct fired gas turbine. All of them emphasized the problems which plagued previous projects of this kind. In 1944 the Locomotive Development Committee of Bituminous Coal Research, Inc., was formed to study the problems of combustion, coal handling, and fly ash removal which would have to be solved before coal could be used to fire a gas turbine. By 1947 this committee was composed of the chief executive officers of nine eastern railroads and five eastern coal companies. All of the members of this committee were vitally concerned in a coal fired gas turbine because coal cost only one-fourth as much per heat unit as fuel oil. A number of research projects were started to develop and test components on a small scale. This included work at John Hopkins University, Battelle Memorial Institute, Institute of Gas Technology at Chicago, Purdue University, and Southern Research Institute. By 1946 a pilot plant had been installed at the Dunkirk, New York plant of Alco Products Div. of American Locomotive Co. The U. S. Bureau of Mines made available to the Locomotive Development Committee (hereafter called LDC) a Houdry process gas turbine plant, originally destined for a Russian oil refinery. The full scale pilot plant was used to evaluate the results obtained from the small scale studies under actual gas turbine conditions. Operation of this plant disclosed a number of problems which had not been discovered in the small scale tests. By 1951 four 250 hr tests had been conducted with the Houdry gas turbine to test out a variety of equipment. The major problem concerned the removal of abrasive fly ash from the products of combustion so that wear on turbine blades would not be excessive. The first 250 hr test showed that the original fly ash separating equipment was inadequate. Large ash particles passing through the turbine blading were nicking the leading edges of the first row blades. At the conclusion of the second 250 hr test, erosion was so severe that the first row of stator and the first row of rotor blades were replaced. At the end of the third 250 hr test, it was necessary to replace the first three rows of stator blading. The fourth test was used to test out a new design fly ash separator developed by LDC and named the Dunlab tube. This device gave more encouraging results than any of the others tested. Early enthusiasm for overcoming major difficulties had resulted in placing an order in 1946 with Allis-Chalmers Mfg. Co. for a 3750 hp regenerative gas turbine. The gas turbine, together with associated combustion and ash removal equipment, coal handling equipment, generators and gear reduction unit was installed at Dunkirk by 1951. A 750 hr test was made in 1952 with the LDC-Allis Chalmers gas turbine power plant. At the end of this test it was necessary to replace the first four rows of both rotor and stator blading. Rows 5 and 6 did not require replacement. In 1953 the American Locomotive Co. joined with LDC and assumed an active role in equipment development and manufacture. During 1954 LDC-Alco operated the rebladed gas turbine 300 hr to determine if a new fly ash separator was adequate. Performance of the improved separator was considerably better, but trouble was experienced with clogged blowdown lines from the Dunlab tubes. When these lines clogged it permitted the passage of abrasive particles. In 1955 a total of 1421 hr was run. This included 243 hr of cycle operation on Union Pacific coal from the D. O. Clark mine at Superior, Wyoming. During the 243 hr a total of 370 tons of coal was consumed. The purpose of this test was to determine if U.P. coal was suitable for use in a coal fired turbine. It was the unofficial opinion that it was as good or better than the eastern coals that had been tested.

Jan 1, 1964

By Roy D. McLellan

Electrolytic production of cadmium at the Great Falls plant started in the first part of the year 1925. Prior to that time, an experimental unit had been in operation for a few months during the year 1922. At present the plant is the largest producer of cadmium, not only in the United States but in the world. Electrolytic cadmium is characterized by its very low content of impurities. The main impurities, which are lead, copper, zinc and iron, do not aggregate more than 0.05 per cent., leaving a cadmium content better than 99.95 per cent. The consumption of cadmium has increased rapidly since the war, with the growing use in the plating industry. Cadmium plating has come into prominence because of its connection with the automobile and radio industries. As a protective coating, a deposit of cadmium is superior to zinc. Cadmium is also used extensively in alloys. Important among these is the alloy with copper used in telephone and trolley wire. In proportion of 0.5 to 1.2 per cent., cadmium adds materially to the strength and wearing qualities. Practically all commercial zinc concentrates contain a small amount of cadmium. In the electrolytic zinc process, the cadmium that is dissolved in the regular leaching operation is removed from solution with metallic zinc, generally added in the form of zinc dust. This precipitate also contains the copper taken into solution and the excess of zinc dust, which is required in order to insure a complete removal of all impurities. The precipitate is treated by a separate process to recover the copper, cadmium and excess zinc. In order to make the metals more soluble and to render insoluble such impurities as iron, arsenic and antimony, the precipitate is roasted. The roasting is carried out in gas-fired McDougall furnaces, with a roasting temperature of about 700' C. The roasted residue is leached with dilute sulfuric acid, spent electrolyte from the zinc electrolyzing, containing 10 to 12 per cent. free H2S04. The leaching is done in cylindrical tanks of 30 tons capacity, agitated

Jan 1, 1930

By Raphael D. Schilz, Michael F. Dunn, Edward D. Thimons, Francis S. Kendorski

During a mine fire or other emergency, it may be desirable to reverse the air flow in order to provide an escapeway or to control a fire. Also, in colder areas, the air flow may be reversed to prevent ice build-ups. When reversing main mine fans, the operator usually does not know what operating characteristics of flow and pressure to expect. Laboratory testing of vane axial main mine fans has been completed in order to establish forward and reverse performance characteristics under controlled conditions, with the results presented here. Preliminary tests under field conditions have also been conducted. The data obtained suggest that reverse performance characteristics are dependent upon the blade angle and the hub to tip ratio. There is also evidence that reverse performance can he predicted for a family of blade angles in a given hub to tip ratio. In general, the air quantity delivered by the fan is 30% to 60% less in reverse than when operating in the normal forward mode.

Jan 1, 1982

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