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By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

Discussion of the paper of F. M. Simonds and E. Z. Burns, presented at the New York Meeting, February, 1913, and printed in Bulletin No. 75, March, 1913, pp. 369 to 402. W. L. SAUNDERS, New York,. N. Y.:-Mr. Burns in his native Colorado modesty has said that he apologizes for things left out of this paper. I am much impressed by what he has put into the paper, as of all the papers that I have read on the subject, describing, as it does, a specific piece of work that has been accomplished, I do not recall one that gives so much information in such a practical way. Mr. Burns has also said that it is very hard to get men to put things down while the work is being driven. My experience is that it is very much harder to get the men in charge of work of this kind to bring them in in the form of a report before a body of engineers after the work is done. We have a great many cases where records are kept in much detail, but they are usually kept under cover, with the mistaken idea that the information gained is private information for the benefit of those who have done the work. Messrs. Simonds and Burns have opened up this case so that we can get the benefit of that experience which they have had, and so that we can learn something for the future. The description contained in this paper, as I have said, is a very practical one. You will notice in going through it. that the authors have given in detail a record of their work from the beginning to the end, and they even go so far as to publish an exact copy of the Rawley Mining Co.'s daily report. That daily report is something which those of us who are engaged in similar work might copy to great advantage, and having it before us we can check up our men while doing work and exact from them equal conditions, if it is possible to do so.

Jan 5, 1913

By Walter B. Lenhart

Introduction and Importance of the Industry Sand, as described in this chapter, is a crude product used for ballast on railroads and highways, and as the fine aggregate in concrete, mortar, plaster and in asphalt paving materials. The sand used in glass, as a molding sand, and as a source of silica is described in Chapter 43. Sand and gravel together constitute the mineral raw materials of largest volume produced from the earth. In 1958, as reported by the U.S. Bureau of Mines,21 680,080,000 tons of sand and gravel (including industrial sand) were produced in the United States. The nearest competitor was crushed rock of which 532,818,000 tons were produced. Coal, both bituminous and anthracite accounted for only 431,616,689 tons in the same year. In dollar value, sand and gravel were exceeded only by cement, crushed rock and fuels. Hence it is a major unit of the mineral-producing industry. As an example, one plant in California operates around the clock at an average rate of 1,500 tons per hour, and at peak intervals has shipped over 4,000 tons per hour, all by trucks. Nevertheless, it is controlled by one man through a panel of push buttons that control the crushing, screening, washing, grading, stock piling, and reclaiming of the products. Because sand and gravel are low-valued commodities, but are used in every construction undertaking in every city, village, farm, dam and highway, they are produced in almost every county in the United States and southern Canada, by thousands of individual operators, very few of whom operate in more than one community. Many operations, particularly those established to supply the needs of major dams that are under construction, or of major segments of new highways, are temporary in nature, and the equipment installed is more or less portable. Because of the bulky nature of sand and gravel, there is very little interstate movement, and almost no exports or imports, except a little movement back and forth across the border of the United States and Canada. First, the material needs definition. Definitions Sand and gravel have been defined as continuously graded unconsolidated materials that appear in the earth's surface as a result of the natural disintegration of rocks. Both normally appear together, but in a wide variety of sizes, types and range of size classification. The American Society for Testing Materials has tentatively revised its definition of "sand" as: granular material passing the 3/8-in. sieve and almost entirely passing the No. 4 (4760-micron) sieve and predominantly retained on the No. 200 (74-micron) sieve, and resulting from natural disintegration and abrasion of rock or processing of completely friable sandstone (ASTM Designation C 58-55T). The Society's tentative revision of its definition of "gravel" is: granular material predominantly retained on the No. 4 (4760-micron) sieve and resulting from natural disintegration and abrasion of rock or processing of weakly bound conglomerate (ASTM 125-55T). Sand and gravel deposits contain materials from the finest silt to the largest boulders. Chemical definition of the two materials is nearly impossible. Sand and gravel always are

Jan 1, 1960

By W. F. Holbrook, T. L. Joseph

The problem of sulfur control is important in all blast-furnace operations but particularly for certain grades of steel because of the rigorous specifications. During the past decade the tendency has been to produce pig iron and hot metal of lower sulfur content. As most of the sulfur in the iron originates in the fuel, the use of high-sulfur coke demands modifications in practice to meet sulfur specifications. While it is generally known that high temperatures and more basic slags favor desulfurization, operators as a rule produce the most acid slag that will permit proper desulfurization. The viscosity of blastfurnace slag has been thought to be related to desulfurization and has been investigated by Feild and Roysterl, also McCaffery and his associates*, but apparently no systematic effort has been made to determine the relative desulfurizing powers of slags over the range of composition encountered in practice. Development of Testing Method Because slag and metallic iron are immiscible, the desulfurization reaction is heterogeneous, occurring only at the interfaces between slag and metal bodies. In the blast furnace the newly reduced iron, containing FeS, descends through the slag bath probably either as small drops or streams, at the interfaces of which desulfurization occurs. After its descent through the slag the iron collects to form a bath of metal, at the top surface of which desulfurization reaction probably occurs. These two steps have been thought to account for all desulfurization in the blast furnace. Kinney3 found that metal removed from the blast furnace just above the tuyeres contained three to four times as much sulfur as the iron at cast. Herty and Gaines4 conclude that most of the sulfur is removed while the metal is passing through the slag. Mund, Stoecker

Jan 1, 1936

By W. F. Holbrook, T. L. Joseph

The problem of sulfur control is important in all blast-furnace operations but particularly for certain grades of steel because of the rigorous specifications. During the past decade the tendency has been to produce pig iron and hot metal of lower sulfur content. As most of the sulfur in the iron originates in the fuel, the use of high-sulfur coke demands modifications in practice to meet sulfur specifications. While it is generally known that high temperatures and more basic slags favor desulfurization, operators as a rule produce the most acid slag that will permit proper desulfurization. The viscosity of blastfurnace slag has been thought to be related to desulfurization and has been investigated by Feild and Roysterl, also McCaffery and his associates*, but apparently no systematic effort has been made to determine the relative desulfurizing powers of slags over the range of composition encountered in practice. Development of Testing Method Because slag and metallic iron are immiscible, the desulfurization reaction is heterogeneous, occurring only at the interfaces between slag and metal bodies. In the blast furnace the newly reduced iron, containing FeS, descends through the slag bath probably either as small drops or streams, at the interfaces of which desulfurization occurs. After its descent through the slag the iron collects to form a bath of metal, at the top surface of which desulfurization reaction probably occurs. These two steps have been thought to account for all desulfurization in the blast furnace. Kinney3 found that metal removed from the blast furnace just above the tuyeres contained three to four times as much sulfur as the iron at cast. Herty and Gaines4 conclude that most of the sulfur is removed while the metal is passing through the slag. Mund, Stoecker

Jan 1, 1936

By T. D. Mueller

Many investigators have used the response of the "dimensionless aquifer" to a unit pressure drop or a unit fluid-withdrawal volume to calculate the performance of an aquifer in supplying water influx to an oil reservoir. In the past, these response functions have been calculated with the aid of the Laplace transform. With the advent of ultra highspeed digital computers, it becomes practical to solve for the response functions with finite-difference techniques. The computer method also permits extension of the dimensionless-aquifer concept to include the nonhomogeneous aquifer wherein the permeability and other properties vary as a function of the space co-ordinates. This paper gives results of calculating the response functions for a series of nonhomogeneous aquifers. Response functions are presented for both linear and radial aquifers whose thickness, permeability-viscosity ratio and porosity-compressibility vary. These functions are new and should prove useful to the petroleum engineer in analyzing the behavior of nonbomogeneous aquifers. Results are presented in the form of charts that can be easily used by the field engineer. INTRODUCTION Aquifers which surround many oil and gas reservoirs have the ability to supply water influx to such reservoirs as oil and gas are withdrawn. This water influx, called natural water drive, provides one of the most effective driving mechanisms for the production of oil and gas. In producing a reservoir, therefore, it behooves one to make the maximum use of natural water drive. To achieve the maximum use, the reservoir engineer must be able to predict the performance of an aquifer under a variety of production schemes that may be proposed for the reservoir. Unfortunately, the physical properties which dictate aquifer behavior often are known only within limits. Seldom do wells penetrate the porous strata of the aquifer. Even when they do, quantitative information regarding porosity, permeability and water compressibility is seldom available. It is known, however, that the water efflux from most aquifer systems is governed by a single, relatively simple, linear, partial differential equation. Also, the general physical location of the aquifer boundaries often are known. A technique originall proposed by Hurst1 and van Everdingen and Hurst2 has been found useful in analyzing reservoirs in this situation. The idea was later expanded by van Everdingen, Timmerman and McMahan3 to include the mathematical technique of least-squares fitting. This latter method will be referred to as the VTM method. The basic assumptions of the VTM method include the following. 1. The location of the physical boundaries of the aquifer are known. 2. The flow conditions at these physical bound-daries are also known. 3. The aquifer is homogeneous; e.g., thickness, permeability, water compressibility and porosity are constant throughout. In the VTM method, a material balance is made on the fluids entering and leaving the reservoir. In the balance equations, the water-influx term is represented as the product of the water influx from an arbitrarily-selected, dimensionless aquifer system times an unknown conversion number. This balance can be formed as many times as there are data points in the history of the reservoir. Each time, the conversion number can be evaluated. If the reservoir engineer has picked the correct dimensionless aquifer to represent the real aquifer, the conversion number remains constant for all balances that have been made over the history period. If such a situation occurs, the reservoir engineer can then predict the performance of the reservoir for any type of production scheme by using the function associated with that particular dimensionless system and the derived conversion number. These functions will be referred to as the response function of the aquifer. If the aquifer is nonhomogeneous (e.g., if the porosity, permeability, thickness, porosity, or

By Henry P. Ehrlinger

The Alta and St. Louis mines of the Alta Mines, Inc., produce a somewhat oxidized ore with a talc gangue that presents quite a problem in milling. For several years the mill recoveries were relatively low and there seemed to be no cure for this condition even with increasing the various collecting agents and frothers to two or three times of what they should be. The usual alibi of "oxidized ore" was given as the reason for these results and the matter stood there for some time until these investigations were started. Flowsheet As a brief outline of the flowsheet the ore is crushed to minus I in. in a Telsmith jaw crusher and then fed to a 64½ Marcy grate mill. The resulting product from the grate mill is passed over a trommel where the coarse particles (plus 7 mesh) are returned to the grinding circuit through the classifier. The under 7-mesh pulp is passed over two Denver mineral jigs where a high grade concentrate is produced, thence over two Wilfley tables where a table concentrate is produced and about 80 pct of the oxide lead recovered. The tailings from these tables are pumped back to the classifier and after classification the 30 pct pulp density product, which overflows the lip, is passed into a series of 10 Denver economy flotation cells where a lead-copper concentrate is produced. Three products are made and shipped to the smelter termed jig, table and float concentrates. Results with various Reagents In March of this year work was started on the metallurgical problems of the mill and, as is shown in Table I, the results obtained were not too efficient. Tests were run with various reagent combinations that were recommended for ores of this nature but there was no appreciable effect on the recoveries. The grades of the flotation concentrates were reduced by the insoluble picked up and retained by these more powerful collectors and frothers. Results with "Metso" In past work on ores of this type the use of "Metso" had improved gold and lead recoveries, but no effect on the silver and copper recoveries had been noted. To

Jan 1, 1949

By Henry P. Ehrlinger

THE Alta and St. Louis mines of the Alta Mines, Inc., produce a somewhat oxidized ore with a talc gangue that presents quite a problem in milling. For several years the mill recoveries were relatively low and there seemed to be no cure for this condition even with increasing the various collecting agents and frothers to two or three times of what they should be. The usual alibi of "oxidized ore" was given as the reason for these results and the matter stood there for some time until these investigations were started. FLOWSHEET As a brief outline of the flowsheet the ore is crushed to minus I in. in a Telsmith jaw crusher and then fed to a 64 1/2 Marcy grate mill. The resulting product from the grate mill is passed over a trommel where the coarse particles (plus 7 mesh) are returned to the grinding circuit through the classifier. The under 7-mesh pulp is passed over two Denver mineral jigs where a high grade concentrate is produced, thence over two Wilfley tables where a table concentrate is produced and about 80 pct of the oxide lead recovered. The tailings from these tables are pumped back to the classifier and after classification the 30 pct pulp density product, which overflows the lip, is passed into a series of 10 Denver economy flotation cells where a lead-copper concentrate is produced. Three products are made and shipped to the smelter termed jig, table and float concentrates. RESULTS WITH VARIOUS REAGENTS In March of this year work was started on the metallurgical problems of the mill and, as is shown in Table I, the results obtained were not too efficient. [ ] Tests were run with various reagent combinations that were recommended for ores of this nature but there was no appreciable effect on the recoveries. The grades of the flotation concentrates were reduced by the insoluble picked up and retained by these more powerful collectors and frothers. RESULTS WITH "METSO" In past work on ores of this type the use of "Metso" had improved gold and lead recoveries, but no effect on the silver and copper recoveries had been noted. To

Jan 1, 1947

By J. L. Huitt, S. R. Darin

The use of a partial monolayer of propping agent to obtain a high flow capacity for a hydraulically induced fracture is discussed. From the results of laboratory work it was shown that a modified form of the Kozeny-Carman relation could be used to describe the flow in the partial monolayer propped fracture. With equations presented in the paper, the density pattern of the propping agent (number of particles per unit of fracture surface) that results in the maximum flow capacity for the fracture can be determined. The maxitnum flow capacity obtained with a partial monolayer is often an order of magnitude greater than the flow capacity obtained in greater width fractures containing multilayers of the propping agent. INTRODUCTION One of the predominant factors controlling the success of a hydraulic fracturing operation is the propping of the fracture. The trend in hydraulic fracturing recently has been an increase in the ratio of propping agent-to-fluid. The primary purpose of this increased ratio is to sustain a propped fracture of greater width. It was shown in a recent study' that for some formations low concentrations of propping agent would result in "closing" or "healing" of the fracture. In some cases, in an effort to insure sufficient propping agent concentration, the fracturing operation is designed to obtain a pack of the propping agent in the fracture. The placing of a pack of propping agent in the fracture provides a fracture of maximum width; however, the width alone does not control the flow capacity of the fracture. The flow capacity is dependent on the permeability of the fracture, as well as the fracture width. Thus, increasing the permeability to obtain larger flow capacities is as important as obtaining a greater width fracture. By increasing the concentration and particle diameter of the propping agent, fractures of sufficient flow capacities are obtainable for effective well stimulation in a number of formations. However, in some of the recovery techniques, the fracture capacity obtained by commonly used practices in fracturing is inadequate. One such recovery technique is gravity drainage via a horizontal fracture placed near the base of the productive zone. For this recovery technique, the fracture capacity desired is usually one to two orders of magnitude greater than the fracture capacity normally obtained in fractures propped with the size of sand commonly used (20-40 mesh). By the use of particles of larger diameter, the permeability of a pack2 is increased; however, even a multilayer pack results in a fracture flow capacity lower than that desired for some formations. For example, a fracture of 1/4-in. width, packed with 8-12 mesh sand of about 2,000 darcies permeability, would result in a fracture flow capacity (permeability X fracture width) of only 40,000 md-ft. If the fracture flow capacity needed is an order of magnitude greater than that cited in the example, an approach different from the formation of a pack in the fracture is needed. One approach is a partial monolayer of large-diameter propping agent. In working with this type of fracture system, it was found that the flow problems were unique to the system; therefore, the study discussed in this paper was made. THEORY AND RELATED STUDIES Previous studies, although related to that described in this paper, have not pertained directly to the flow in a fracture propped with a partial monolayer of propping agent. However, studies such as flow between parallel plates,' flow in packed columns,' fracture flow capacity' and flow in simulated fractures reduce the scope of this flow problem considerably. A fracture propped with a partial monolayer of dropping agent may be considered to be between two extremes — between an open fracture and a bed of particles packed In a conduit of fracture geometry. Thus, it seems appropriate to review the extreme cases.

By C. van der Poel, R. L. Chuoke P. van Meurs

When an initially planar interface between two im-ttitcihle liquids is displaced at constant rate, U, nor-mat to the front, instability will occur for all rates greater than a critical rate. U, given by provided the Fourier decomposition of the spatial pertmrbcrtiott or deformation of the moving displacetment front contains modes with wavelengths. A, greater than a critical wavelength, given by tit there expressions, p, p and k, with the subscripts I and 2 distinguishing the two 1iquids under consideration, are density, viscosity and effective pemeability coefficients respectively; g is the absolute value of the acceleration due to gravity; and cos (zz') is the direction cosit7e between the vertical carlesian coordinate z' (positive upward) and the z coordinate norma1 to the initially plane macroscopic interface taken positive in the direction from Liquid I to Liquid 2. U is the average volumetric velocity (injected volume of liquid pet. unit time per unit of area normal to Z) and is positive for Liquid I displacing Liquid 2, negative for the reversc displacement and r2 is an effective inter-fucial tension (for displacements between parrallel plates, t0= s the ordinary bulk interfacial tension). further, there is a wavelength of maximum instability given by For natural perturbations, this wavelength will preclotninate and characterize the form of the instability as a quasi-sinusoidal deformation, i.e., viscous fitzgers of peak-to-peak separatiotr, A,,. Comparison of experitient with theory rei'eals tltat these considerations are recsonably valid for displacements in hoth parallel plate chantzels and nnconsoli-clutt'd glass ptnvder packs. These results are. tij particular interest for interpretation of data from laboratory experiments with regard to fielil applica/iotz.s. It is quite possible for A,, although st7zall relative to the large lateral dimension of the reservoir, to rxceed the greatr.st lateral extent of the lahoratory sample or model. If it does, frontal displace- ment occurs in the laboratory experiments, and oil INTRODUCTION Thc puposes of this paper are to present theoretical and experimental evidence for occurrence of macroscopic instabilities in displacement of one viscous fluid by another immiscible with it through a uniform porous medium and to compare available experimental data with some predictions of a theory of instability developed by the first author. The instabilities are referred to as macroscopic in the sense that spatially quasi-sinusoidal, growing fingers of the displacing liquid are formed, the width and peak-to-peak separation (wavelength) of which is large relative to a characteristic length of the particular permeable medium such as grain size. Visual models of two kinds have been used to obtain observations: displacement of oil by water-glycerine solutions through the flow channel formed by closely spaced parallel plates and displacement of oil by water with and without initial interstitial water through unconsolidated glass powder packs, employing the technique of matching indices of refraction. In all cases we have observed macroscopic instabilities or fingers under conditions predicted by the theory to be favorable for their occurrence. The phenomenon discussed here is not the production of streamers due to gross inhomogeneities such as permeability stratification of the porous medium. It is our object to show, on the contrary, that a quantitative prediction of finger spacing is possible in a porous medium known to be macroscopically homogeneous and isotropic throughout. The importance of the phenomenon in its influence on the configuration of oil and water with respect to oil production behavior was noted earlier by Engel-berts and Klinkenberg' who coined the term "viscous fingering". THEORY Necessary and Sufficient Conditions ior Instability anc Initial Kinematics There are several levels of increasing complexity in the theoretical description of instabiIity of fluid displacements in permeable media. Of these, the simplest description, ;tdapted to low permeability systems, is selected for presentation.' More inclusivc tlescriptions are reserved for separate publication.

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By R. L. Loofbourow

We are concerned with the destabilizing effects of water inflow and remedies which can be used to reduce that cause. The number of these remedies which have already been demonstrated in mining may be a surprise. Several possible remedies, well known in other work seem worth trial. In saw mines the destabilizing effect of inflow is negligible; in others it can be disaster. Inflow can reduce stability in mining for very nearly, if not all minerals, whether by open pit or under- ground methods. It might cause trouble in saw under water work. As examples of these effects consider hydrostatic pressure on the walls of fractures and ' lubrication' of clay seams. Skin protection by paint or gunite is not likely to help. It is generally necessary to go deeper, for example to drain the ground more effectively or to reduce inflow. The improvement of stability is but one of a score of possible advantages attainable with water control. Most of these advantages would help costs as wet mines go deeper for leaner ore while coping with more restraints and higher costs of per, labor and supplies. Investigation is promising!

Jan 1, 1983

By Albert Williams

A large proportion of the work performed in wet-crushing silver mills is devoted to the handling and re-handling of pulp between the battery and the pans. There seems to be no generally applicable substitute for the settling-tanks, and in the present system of constructing mills the tanks involve an amount of labor which may be regarded as disproportionate and unnecessary, in view of the automatic improvements which have been introduced in other directions. This diffculty has been met, however, by Boss's continuous process, in which the pulp flows directly from the mortars to the first of a series of constantly working overflow-pans. This method has been adopted at the Noonday mill, Bodie, California; the Harshaw, Arizona; the Sierra Grande, New Mexico ; and the Prietas, Sonora. The continuous process, while giving excellent results with special ores, and under peculiar local conditions (such as a deficiency in water supply), is not, I believe, claimed to be available for all raw-amalgamating mills, notwithstanding its well-merited popularity for certain work. Some trouble has been experienced from the tendency to concentration in the pans, though this can be avoided by skilful manipulation. It has also the disadvantage inherent in combinations of distinct operations ; it requires a very nice adjustment of the water supply to obtain full battery efficiency without running the pans too thin, though the latter defect is partially compensated for by the gradual thickening of the pulp as it proceeds through the series of pans. The objection is similar to that which holds in a parallel duplex process, that of combining roasting and smelting in a single furnace, where each operation is injuriously affected by the necessity of fitting it in with another and entirely different one.

Jan 1, 1883

By W. M. Weigel

THE rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago, have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used, in its natural state after mechanical preparation only (such as. grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the eastern and northern states. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The southern states have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the north, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business. revives and freight rates are adjusted.

Jan 2, 1922

By Henry Siegmann

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

Jan 1, 1976

By P. E. McKinney

DEVELOPMENTS in engineering during the past decade, particularly as applied to marine construction, mining machinery and other purposes in which corrosion offers a serious problem, have created a large demand for a non-ferrous metal highly resistant to corrosion and at the same time useful in general construction work as a substitute for steel without materially decreasing the factor of safety or increasing the weight of the various parts over that ordinarily used in the case of mild steel. To obtain the combination of desired properties many compositions have been proposed and used with excellent success, but at the present time probably the most popular and most widely used combination is the non-ferrous alloy commonly called manganese bronze. This is nothing more than a high brass to which have been added, by the proper method of alloying, comparatively small percentages of aluminum, iron, or manganese with the definite purpose in view of strengthening the alloy and rendering it more dense and close-grained than the average yellow-brass casting. In the manufacture of manganese bronze a great deal has been said about the importance of using only the highest grades of raw material and the beneficial or detrimental effects, as the case may be, of various impurities, as well as the importance of adding the ingredients according to various formulas proposed; but in most of these cases the literature on the subject has dealt principally with the manufacture of this alloy from virgin metals And raw materials of the highest purity. It is the purpose of this paper to deal particularly with the possibilities that lie in the proper development of methods for manufacturing such an alloy by more economical methods than those which have usually been discussed in other literature on the subject. Shortages have recently existed in raw materials needed for many products entering into the various branches of engineering work, particularly the non-ferrous metals, and during the next few years of reconstruction the country will be flooded with many

Jan 2, 1919

By P. E. McKinney

Developments in engineering during the past decade, particularly as applied to marine construction, mining machinery and other purposes in which corrosion offers a serious problem, have created a large demand for a non-ferrous metal highly resistant to corrosion and at the same time useful in general construction work as a substitute for steel without materially decreasing the factor of safety or increasing the weight of the various parts over that ordinarily used in the case of mild steel. To obtain the combination of desired properties many compositions have been proposed and used with excellent success, but at the present time probably the most popular and most widely used combination is the non-ferrous alloy commonly called manganese bronze. This is nothing more than a high brass to which have been added, by the proper method of alloying, comparatively small percentages of aluminum, iron, or manganese with the definite purpose in view of strengthening the alloy and rendering it more dense and close-grained than the average yellow-brass casting. In the manufacture of manganese bronze a great deal has been said about the importance of using only the highest grades of raw material and the beneficial or detrimental effects, as the case may be, of various impurities, as well as the importance of adding the ingredients according to various formulas proposed; but in most of these cases the literature on the subject has dealt principally with the manufacture of this alloy from virgin metals and raw materials of the highest purity. It is the purpose of this paper to deal particularly with the possibilities that lie in the proper development of methods for manufacturing such an alloy by more economical methods than those which have usually been discussed in other literature on the subject. Shortages have recently existed in raw materials needed for many products entering into the various branches of engineering work, particularly the non-ferrous metals, and during the next few years of reconstruction the country will be flooded with many

Jan 1, 1919

By Don Blackmar

THE production of non-ferrous secondary metals has become a large and important industry in the United States, and deals with practically every type of manufacturing concern.. Its business is unique in that it generally buys from its customers as well as sells to them, whether they are individuals, cities, corporations, or the United States government. Its operations are of vital importance to the success and prosperity of many of the nation's most important manufacturers; yet there are few industries about which less is generally known by those outside it, whether concerning the magnitude of its operations or the details of its actual technique. The industry itself is to blame for this meager publicity, because its technical men have made few attempts to openly exchange ideas, in spite of the excellent examples set by the iron and-steel or the copper and brass industries. Whether this is due to the ancient shroud of secrecy generally supposed to cover smelting operations, or because its technical men actually felt that the industry was too puny to be interesting, is hard to say. This paper will consider its subject in a 'general way, attempting to show something of the size and importance of the industry, as well as its fitness to do its work well. Attention will be called to the sound economic reasons for the handling of non-ferrous wastes by specialists, and to the often unseen losses of metals and labor which occur when manufacturers reclaim' their own metallic wastes.

Jan 1, 1928

By Don Blackmar

THE production of non-ferrous secondary metals has become a large and important industry in the United States, and deals with practically every type of manufacturing concern. Its business is unique in that it generally buys from its customers as well as sells to them, whether they are individuals, cities, corporations, or the United States government. Its operations are of vital importance to the success and prosperity of many of the nation's most important manufacturers; yet there are few industries about which less is generally known by those outside it, whether concerning the magnitude of its operations or the details of its actual technique. The industry itself is to blame for this meager publicity, because its technical men have made few attempts to openly exchange ideas, in spite of the excellent examples set by the iron and steel or the copper and brass industries. Whether this is due to the ancient shroud of secrecy generally supposed to cover smelting operations, or because its technical men actually felt that the industry was too puny to be interesting, is hard to say. This paper will consider its subject in a general way, attempting to show something of the size and importance of the industry, as well as its fitness to do its work well. Attention will be called to the sound economic reasons for the handling of non-ferrous wastes by specialists, and to the often unseen losses of metals and labor which occur when manufacturers reclaim their own metallic wastes.

Jan 1, 1928

By J. H. Bechtold

Tensile properties of annealed molybdenum were investigated from 1000" to—200°C. In the vicinity of room temperature a well-defined transition in tensile properties occurs. Reduction in area decreases from over 80 pct to 0 pct and, simultaneously, the yield strength increases about 60,000 psi. MOLYBDENUM, tungsten, iron, and many other metals and alloys with the body-centered cubic and hexagonal close-packed crystal structures change from ductile to brittle behavior over some relatively narrow temperature range. The temperature at which this transition in ductility occurs depends on chemical composition, microstructure, and method of testing. When fine grained, completely recrystallized molybdenum of commercial purity is tested in uniaxial tension at a slow strain rate, the transition occurs at slightly below room temperature.' Iron2 and tungsten3 tested under similar conditions become brittle at temperatures close to the boiling point of nitrogen, — 195°C and at about 200°C, respectively. A sharp change in ductility is uncommon in metals with the face-centered cubic crystal structure, however, a relatively sharp transi- tion in notched bar impact properties has been observed below room temperature in a face-centered cubic copper-antimony alloy.4 A transition from ductile to brittle behavior is usually explained by the concepts originally developed by Ludwik,5 and discussed and elaborated on by others including Orowan,6 Hollomon and Jaffe,7 and Gensamer8 In brief, there are two aspects to strength, first the resistance to flow and second the resistance to fracture. Both are functions of temperature, strain, strain rate, stress system, composition, and microstructure. With decreased test temperature the flow stress required to initiate plastic deformation increases more rapidly than the fracture strength and brittle fracture occurs at that temperature where the yield strength equals or exceeds a brittle fracture strength. This investigation was conducted to determine the effects of temperature, strain, and rate of straining on the flow and fracture strengths of molybdenum above, through, and below the ductile-to-brittle transition. Other variables were held constant during testing. This information is believed to show

Jan 1, 1954