Search Documents

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By William H. Shockley

There was an extensive mining and industrial exploitation of Russia, about 20 years ago, by Belgian, French and British capitalists; but the results were discouraging. It is said that the Belgian and French public together lost approximately $400,000,000, chiefly in the coal and iron industry of southern Russia. This loss is largely accounted for by the fact that most of the companies were formed, as usual in " boom" times, to sell stock; and that thorough investigations were not made. I11 1906, renewed interest was taken in Russian mines, especially in those of gold and copper, and a considerable literature is growing on this subject; but as yet I have seen no account of one of the large Russian mining estates. The following notes on such property, where the conditions are so different from those in the mining regions of the United States, should be of interest: This inadequate and probably somewhat inaccurate account is made up, partly from my own notes made on the ground, in the summers of 1904 and 1905, and partly from a volume on the geology and resources of the estate issued several years ago, containing surface- and mine-maps, and from a pamphlet published in 1904, giving a general account of the condition and prospects of the property. This pamphlet includes a report made in 1899 by Arthur L. Pearse, a member of this Institute. Both these books are in Russian, and were prepared by the Bogoslovsk Mining Co., which owns and operates the property. Articles in many other languages have appeared dealing with various matters connected with the estate; but I know of no other general account of it. In numerous books and articles on the Urals and Siberia, however, localities are described in which somewhat similar conditions prevail. Recent papers by

Jan 1, 1909

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

THE composition and quality of finished steel depend upon selection and proportioning of the raw materials of the charge as well as on control of furnace practice. This chapter deals only with those raw materials of the basic open-hearth process which are important in determining the composition of the steel or slag. They are the metallic charge, oxygen-bearing materials, fluxes, and alloying and deoxidizing additions. Refractories, which may also affect the slag composition, are discussed in the previous chapter. Wide variations are possible in the type and composition of charged materials, but in all cases certain fundamental relationships among the elements of the charge must be maintained. Since the process consists essentially of refinement by oxidation of undesired elements, a balance must be established between the sources of oxygen and the elements in the charge that are subject to oxidation (see Chapters II and VII). For example, if it is desired to use a high ratio of blast-furnace hot metal to scrap, it is necessary to add an oxygen-bearing material such as ore or mill scale to eliminate the excess carbon and silicon that are present in the hot metal. An example of the opposite extreme would be the use of a metallic charge composed entirely of steel scrap. With this type of charge, it is common practice to substitute burnt lime for limestone as a flux and to charge some carbonaceous material such as coke to avoid an excess of oxygen in relation to the elements of the charge that are subject to oxidation. Elements such as copper and nickel, which are not subject to oxidation or other reactions resulting in their elimination, may be introduced into the charge only to the extent to which they are permissible in the finished steel. An example of adjustment of the charge for elements of this type would be found in the use of steel scrap high in copper. In this case, metallic components of the charge other than the scrap should below in copper, or a sufficiently high ratio of pig iron to scrap should be charged to dilute the copper from the scrap, so that the average copper content of the melt will be below the required maximum.

Jan 1, 1944

By J. R. Low, M. Gensamer, W. T. Lankford

THE problem of sheet metal formability is one which has received a vast amount of attention during recent years. In spite of the great amount of study and experimental work which has been devoted to this problem, many of its fundamental aspects are still not well understood. No generally satisfactory test has been developed which is capable of providing a reasonably adequate evaluation of sheet metal formability, particularly in borderline cases. Anomalies persistently arise in which a lot of supposedly satisfactory material exhibits excessive breakage when formed. This lack of suitable technological tests greatly hinders the design of new parts and the substitution of new materials in parts of existing design, frequently necessitating considerable costly trial and error experimentation on an actual production basis. When, at the beginning of World War II, it became apparent that mass production methods of forming would be required in the aircraft industry if the large numbers of military aircraft needed were to be supplied, renewed attention was focussed on the problem of sheet metal formability. It was widely recognized that the formability requirements placed on sheet metals had been steadily increasing in severity through the years, especially as greater and greater emphasis was placed on streamlined designs with the resultant freer application of doubly curved surfaces. The recent advent of several new high strength aluminum alloys of more limited formability than some of the older alloys also served to emphasize the need for new approaches to the problem. It seemed evident that progress in the technology of sheet metal forming would depend to a great extent on the development of more reliable criteria for the evaluation of formability. Although the problem is admittedly very complex, the most logical approach appeared to be through studies of the fundamental material properties of sheet metals, especially under complex stress conditions simulating those prevailing in actual forming operations. Most previous investigations have failed to make full use of existing knowledge of fundamental material properties, and in many instances have attempted correlations with properties which are now recognized as being ambiguous in nature. This investigation was undertaken, therefore, with the aim of developing methods for the study of the flow and fracture of sheet metals under combined stresses, and of making use of such methods as might be developed in

Jan 1, 1947

By Clarence Zener

Contents Page General Principles................................................................. 551 Equilibrium Diagrams......................................................... 551 Nucleation................................................................... 553 Kinetics of Phase-boundary Propagation......................................... 553 Kinetics of Growth of New Phase............................................... 556 Spheroidization............................................................... 560 Pure Iron-carbon System........................................................... 561 Formation of Pearlite.......................................................... 561 Interlamellar Spacing........................................................ 562 Pearlite C-curve............................................................. 563 Bainite Formation............................................................. 565 Formation of Martensite....................................................... 570 Loss of Tetragonality of Martensite.............................................. 570 Effect of Alloys upon Decomposition of Austenite..................................... 572 Pearlite...................................................................... 572 Bainite and Martensite......................................................... 574 Time-temperature-transformation Curves............................................. 576 Appendix A............................................................. ......... 579 Appendix B....................................................................... 580 Appendix C....................................................................... 580 The present investigation started in an attempt to understand certain details of the decomposition of austenite, and of the effect of alloying elements thereon. As the investigation proceeded it became apparent that not only these details, but all the general features of austenite decomposition, could be understood in terms of fundamental physical principles. Since the direct applicability of these physical principles has not been previously recognized, it was decided to incorporate the original results of the investigation into a review of the general subject of the kinetics of austenite decomposition. This review constitutes the present article. An extended summary of the results is given on pages 576 to 579. This article, which deals with the kinetics of phase transformations, may appropriately be considered as a sequel to two recent articles1,2 from this laboratory on the equilibrium relations in medium alloy steels.

Jan 1, 1947

By C. A. Heiland

Geophysical methods are playing an ever increasing part in various engineering fields. About ten years ago, geophysical exploration was first applied in civil engineering to the study of foundations and the location of construction materials and water. Its usefulness is now being extended into the field of structural engineering. Almost every structure has to be so designed that it will withstand any force to which it may be subjected. Such forces may result from its own weight, applied loads, pressures of various kinds, including those due to wind and water, ground subsidence and vibrations. The last two, problems involving the nature and dynamic behavior of surface and subsurface formations, are within the scope of geophysical investigations. In the design of any structure, the disposition and dimensions of its members as well as their materials must be so selected that they will withstand any or all of the forces enumerated above. In other words, its "resistance" to such forces must be sufficient, allowing for a definite margin of safety. Often a static treatment of the problem leads to satisfactory results, but the static method entails serious errors when vibrations are involved, as in resonance with an impressed vibration the displacements of a structure or parts thereof may dangerously exceed the allowable values. The principle of "dynamic design"† is, therefore, avoiding or reducing resonance by suitable selection of the natural frequency of a structure, or by the provision of damping. Methods of Investigation Dynamic design of structures is required where ground vibrations occur naturally or are produced artificially. Earthquake regions fall in the first group; areas of industrial activity where vibrations are produced by machinery, blasting, etc., fall in the second. In either case, dynamic

Jan 1, 1940

[Pumps: oil-well: plunger: essential parts, G26, 130; 74, 828 improved type, 74, 846 leakage, 74, 837 operating cycle, 74, 833 Uren design, G26, 145 sucker-rod failures, G26, 136 sucker-rod stress, 74, 835 sucker rods, 74, 830, 832 tubing, 74, 833 tubing difficulties, G25, 138; 74, 836 Olivite, 73, 337 valve and seats, 74, 832 Punching: Monel metal, 78, 86 nickel, 78, 86 Punjab. See Indian Empire. PUPIN, M. L biography, M26, 113 John Fritz medalist, 1931, M81, 499 recipient of Washington Award, M28, 155 PURDY, R.: Discussions: on Relative Efficiencies of Domestic Fuels in Relation to Their Costs and Their Advantages 108, 353 on Uses on Coal in the Ceramic Industry, 108,389,398]

Jan 1, 1936

By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By Scott Howard

MANGANESE being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Ar3 transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the Ar3 transformation occurs at a temperature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3 quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Ar3 point as falling to 0° C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer,2 using alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 percent for the manganese content at which Ar3 is depressed to 0° C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By J. S. Osoba, J. W. Graham, P. H. Monaghan

Of the many factors which affect the productivity of hydraudically fractured wells, the wettability of the propping sand has received little attention in the pas/. This paper shows that the wettability of the propping sand is an important factor which shorcltl not he overlooked. An analysis of relative permeability data shows that fractures packed with water-wet sand should be more permeable to oil than are fracturer packed with oil-wet sand. Laboratory results verify this conclusion. Cnlculations show that higher permeability to oil in the fracture should provide higher well productivity. A method is presented which ensures that the propping sand in an induced fracture is water-we1 even though oil is used as the fracturing fluid. The rnethod has been used in more than 150 field jobs: the field resrrlts are discussed briefly. The fluidized nature of water-wet sand in oil has giver1 unexpected benefits. This characteristic of water-wet sand and how it has been used advantageously in field operations are discussed. INTRODUCTION Hydraulic fracturing of subsurface strata to increase the productivity of oil and gas wells has been practiced for about 10 years. Today, fracturing is used more often than any other method of well stimulation. Basically, the process consists of breaking down (fracturing) a subsurface formation with pressure applied by means of a carrier fluid, usually oil or water, and propping the induced fractures apart by means of an agent, usually sand. suspended in the carrier fluid. Currently about 68 per cent of all fracturing is done with a simple mixture of refined oil or lease crude oil and sand'. The research of other investigators has suggested that dry sand is rendered oil-wet when it is contracted with certain types of crude or refined oils.' Hence, it may be expected that some fracturing operations employing an oil as the carrier for sand leave fractures packed with oil-wet sand. Conversely, those operations which employ water as the carrier for the sand probably leave the fractures packed with water-wet sand. Since the permeability of a sand-packed fracture to a mixture of oil and water is dependent upon the wettability of the fracturing (frac) sand, research was undertaken to determine to what extent the wettability condition (water-wet or oil-wet) controls fracture permeability which, in turn, affects well productivity. Additional research was directed toward the development of a method for obtaining the desired fracture wettability. In this report both theoretical and experimental evidence is presented to show the desirability of employing water-wet sand in fracturing operations. A method to obtain water-wet sand is discussed, and field results are reviewed briefly. DEPENDENCE OF WELL PRODUCTIVITY ON FRACTURE WETTABILITY To determine the dependence of well productivity on the wettability of the frac sand, it is necessary to know, first, the effect of fracture wettability on fracture permeability and, second, the effect of fracture permeability on well productivity. The relationship of these variables is considered separately in the order indicated. Effect of Wettability on Permeability Fig. 1 shows relative permeability relations for 20-30 mesh Ottawa sand. Inspection of these curves reveals that the relative permeability to oil when a small amount of water accompanies the flow is considerably higher when water rather than oil is the wetting phase. For

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By Oscar Marzke

STUDIES on the precipitation of a face-centered from a body-centered structure-a common occurrence in alloy systems-are essential to the development of a theory for the formation of segregate structures. The separation of the alpha phase from the beta of the copper-zinc system is an example of this type of precipitation. EARLIER STUDIES ON THE SUBJECT R. F. Mehl and 0. T. Marzke1 in 1931 presented a paper giving the results of some investigations carried out by them on the segregate structures produced when the alpha and gamma phases of the copper-zinc system and the alpha phase of the copper-aluminum system precipi-tate from the beta phases of these systems. They showed that the alpha phase precipitates as needles close to the [111] directions of the beta phase. In the discussion of that paper some doubt was expressed about the nature of the segregate. More investigations were undertaken to determine the character of the precipitate in the copper-zinc system and also the orientation relationship between the matrix and precipitate. The present paper gives the results of these investigations. Since the publication of the earlier paper, several other papers on this subject have been published in this country and abroad. Haneman and Schroder2 reported that the alpha phase precipitates as needles along the [111] directions of the beta phase and that these needles align themselves to form plates on the {111} planes of the matrix. Mathewson and Smith3 pointed out that the {111} plane does not contain the [111] direction and that it would be quite impossible, therefore, for needles in the [111] direction to form plates on the {111} plane. They suggested

Jan 1, 1933

By Frederick Laist

I. EXPERIMENTAL FLOTATION CONCENTRATION INTRODUCTION EARLY in 1914 it was decided to test, on a fairly large scale, the treatment by flotation of Anaconda slime and mill tailing. For this purpose a standard-type Minerals. Separation machine was installed at the Washoe Reduction Works during May and June, 1914. This was followed by the. installation of a full-size Callow pneumatic machine plant. Experiments were also made, on a smaller scale, with the Froment, the Towne, the Fields, and the Anaconda flotation machines. The last-named machine was developed at this plant. In addition to the tests made in the standard-type Minerals Separation machine some tests were made using a Minerals Separation machine of the sub-aeration type. During the series of experiments a large variety of oils was tested. Experiments were also conducted using both round-table feed and tailing to determine whether it would be better to displace the round tables by flotation for the treatment of the slime, or to supplement the round tables by flotation of the round-table tailing. A series of tests was also made on the treatment of the mill tailing by grinding followed by flotation to determine the relative merits of flotation and leaching for the treatment of this product. In addition, flotation tests were made on mixtures of mill tailing and slime. The round-table feed referred to above is the total slime from the mill. It contains about 35 per cent. colloidal solids and approximately 90 to 95 per cent. of the total solids will pass through 200 mesh (0.067 mm.). It assays from 2.3 to 2.6 per cent. Cu. The mill tailing referred to above is the total discard from the mill, exclusive of the slime. It is all finer than 2 mm. and about 90 to 95 per cent. will remain on 0.25 mm. It assays about 0.60 per cent. Cu. A brief summary of the experimental flotation results follows:

Jan 3, 1916

By W. A. Tiller, W. C. Johnston

The solute distribution ahead of an advancing solid-liquid interface is controlled by varying the momentum boundary layer thickness in the liquid adjacent to the interface. Single pass zone-melting experiments on Pb-Sn alloys are described in which the liquid is caused to rotate in the plane of the solid-liquid interface due to the influence of a magnetic .field rotating in this plane. The variation of the diffusion boundary layer thickness with field strength is determined. DURING the freezing of an alloy a partitioning of solute occurs at the solid-liquid interface, the magnitude depending upon the difference in the solid and liquid solubilities at the interface temperature. Because the diffusion coefficient is so small in the liquid relative to normal freezing rates, either a pileup or a depletion of solute occurs at the interface when the partition coefficient, kO, is either less than or greater than unity, respectively. This solute distribution is completely characterized by i) the solute concentration in the liquid far from the interface, C) the ratio of freezing velocityf, to diffusion coefficient, D, iii) the partition coefficient, ko, and iv) the thickness of the diffusion boundary layer, 6,, at the interface (this assumes that an electric field is not applied across the interface). For a particular system, C ko and D are fixed so that the character of the solute distribution can be changed only by a variation of either f or 6c. As is well known, the freezing velocity can be changed by varying the thermal environment of the alloy. Whereas, the thickness of the solute rich layer can be changed by varying the fluid flow conditions in the liquid. It is the purpose of this paper to describe a technique for controlling the fluid flow conditions in the liquid. During most solidification experiments the driving force for fluid flow arises from either mechanical mixing, thermal convection or electromagnetic mixing. The momentum boundary layer thickness, 6m at the solid-liquid interface, within which negligible movement of the liquid occurs, has been calculated for the special case of mechanical mixing where crystals are solidified by the Czochralski technique.l,2 The calculation of 6m for the case of thermal convection has also been made.3 In some calculations it has been assumed that the momentum boundary layer thickness, 6,, may be equated to the thickness of the diffusion boundary layer 6c, at the interface. However, as may be seen from Appendix I this is only true in very special cases and in general where a is a constant of magnitude determined by the particular liquid alloy. Neither calculations nor experimental data exist for the dependence of upon electromagnetic mixing. In this paper experiments are described in which the liquid is caused to rotate in the plane of the interface due to the torque developed on it by a magnetic field, H, rotating in this plane. The variation of is controlled by the variation of H. A magnetic field rotating in a plane perpendicular to the interface has been used for the purification of aluminum. Experimentally, we determined the variation of 5C with H by using the zone-melting technique of pfann5and a theoretical relationship of Burton et a1.2 pfann5 has shown that, after the passage of one molten zone through a long cylindrical charge of uniform concentration, CO, the solute distribution, C,, in the solid is as shown in Fig. 1. The equation describing this distribution is

Jan 1, 1962

By Samuel B. Christy

As is well known, the ore at New Almaden is cinnabar. Native quicksilver occurs also; but, as a rule, in small quantities only. Pyrite occasionally accompanies the ore. Bitumen is quite common,

Jan 1, 1885

By James W. Malcolmson

This paper treats of the history and development of the Sierra Mojada mines in the north of Mexico, the character and extent of the ore-deposits, and the methods of mining the ore. The growth of the smelting industry in Mexico in recent years is, to a large degree, due directly to the output of the lead-bearing ores from the Sierra Mojada mines, and at the present time (1901) new smelters are being built, looking to this district for their supply of lead-ores. These mines are located in the southern part of the State of Coahuila, in the Republic of Mexico, in latitude 27 24' N. and longitude 103O 43' W. of Greenwich. The last account of the Sierra Mojada published in our transactions was contributed by Mr. Richard E. Chism, in October, 1886.* Since that time some 3,000,000 tons of ore have been extracted from the mines, and much additional information has been developed regarding the mineral deposits. Since 1886, the Mexican Northern railroad, 78 miles in length, has been built from Escalon, connecting the camp with the Mexican Central railway, a trunk-line from El Paso, Texas, to Mexico City. The distances by rail from Sierra Mojada to the principal smelting-centers are as follows : To Torreon, Coahuila, Mex., 179 miles; to Monterey, Nuevo Leon, Mex., 422 miles; to El Paso, Tex., U. S., 494 miles; to Aguas Calientes, A. C., Mex., 522 miles; to San Luis Potosi, 8. L. P., Mex., 644 miles; to Pueblo, Colorado, U. S., 1158 miles; to Argentine, Kans., U. S.,

Jan 1, 1902

By G. R. St. Pierre, M. J. Pool, R. Speiser

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult's law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of 'TiCr, is —0.76' lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,' no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were

Jan 1, 1968

By C. L. Bulow

In this discussion of stress-corrosion cracking of widely used copper-base alloys, no attempt has been made to prepare an extensive review or bibliography since this has been quite ably covered by other investigators. An excellent bibliography was published by H. P. croft(1)2 in connection with his studies of stress-corrosion cracking in mercurous nitrate solutions and his analyses of the magnitude and distribution of stresses in brass parts. We are reporting on a few of the results which have been obtained to date in connection with an ammonia vapor test and an alternate immersion test. These are accelerated corrosion tests for determining the susceptibility of materials to failure from season or stress-corrosion cracking due to the presence of moist ammonia and oxygen so prevalent in nature. Our experiences with the ammonia test seem to indicate that it is a more searching test, than the mercurous nitrate test.

Jan 1, 1945