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By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By E. C. Bain

THE more familiar compositions of iron-carbon-chromium1 and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallographic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

By J. H. Moran, E. E. Finklea

The pressure build-up technique is a recognized method of determining permeability from conventional drillstem tests. In this paper an effort is made to extend such techniques to the interpretation of data obtained from the wireline formation tester. Such a study is necessary because of the differences, for this case, in the magnitude of the flow parameters (rate of flow, amount of recovered fluids) and in the flow geometry (flow through a perforation vs flow across the face of the wellbore, etc.) involved in the solution of the equations of flow for compressible fluids. The perforation is replaced by a spherical hole, and the effect of the borehole is neglected, so that the flow can be considered to be radial in a spherical co-ordinate system. Arguments are presented to justify this idealization. Assuming single-phase flow, general relations between pressure and flow rate are developed for a homogeneous medium. The study is then extended to permeable beds of finite thickness. It is shown that the early stages of pressure build-up tend towards spherical flow, while the later stages tend towards cylindrical flow. The thinner the bed, the more quickly flow approaches the cylindrical model. The prevalence of thin beds in practical work makes this analysis quite important. Cases involving permeability anisotropy are treated. INTRODUCTION From wireline formation tester operation, two types of data are obtained: (1) the nature and amount of recovered fluids, and (2) the pressure history recorded during the test. A number of papers have been written dealing with the interpretation of formation production on the basis of the recovered fluids.'.' In general, the methods described have been quite accurate for both high- and low-permeability formations. The present paper will deal with an analysis of the pressures observed. An analysis of the pressure build-up curves obtained in hard-rock country has already been attempted on the basis of the formula proposed by Hor-ner. Although this approach has met with success in many instances, some questions have been raised as to its validity. It is the aim of the present study to place the analysis of pressure build-up in the formation tester on a firmer basis, from which more detailed methods of interpretation can evolve. Because of the great differences between the operation of the wireline formation tester and the conventional drillstem test, modifications are necessary in the interpretation. The major difference relates to the flow geometry. Once the flow geometry has been established other features such as multiphase flow, skin effect, afterflow, etc., well described in the literature, can be introduced. It will be assumed that the mechanical operation of the formation tester is already known to the reader.6 t will suffice here merely to state that the tester provides the means for taking a relatively small sample of the fluid immediately adjacent to the borehole, and for recording the subsequent pressure response. In comparison with conventional drillstem tests, the time required for a satisfactory pressure build-up response is much shorter, because of the relatively small quantity of fluid withdrawn by the wireline tester. This feature is highly desirable in the case of low-permeability formations. For an analysis of the pressure response within the formation, three simple flow geometries are considered— linear, cylindrical and spherical. The spherical and cylindrical flow geometries are most pertinent to the formation tester; therefore, they will receive the major emphasis. Since the configuration of the borehole and the perforation made by the tester complicate the flow geometry, it is necessary to allow for them in the drawdown response. However, because of the volume of formations contributing to the pressure-response, the details of the perforation shape are unimportant in the build-up period. Since relatively small amounts of fluid are withdrawn from the formation, in contrast to a conventional drill-stem test, a study of the "depth of investigation" and the significance of drawdown as well as build-up data will be included. Because the "depth of investigation" will be shown to be rather large, the effect on the build-up curves of the finite thickness of the permeable bed is considered. It is this consideration that leads to the importance of cylindrical flow geometry. Also included is a discussion of permeability anisotropy and its effect on the interpretation of the tester results. The pressure curves recorded by the formation tester will follow two general patterns, depending upon whether the formation is of high or low permeability. Fig. I (a and b) schematically illustrates these two responses. In Fig. 1(a), the high pressure recorded during fill-up of the tool is essentially the pressure differential across the choke in the system. In Fig. l(b), the flow rate is

By Edward Wisser

The environment of an ore body is taken to mean not only its physical surroundings but every factor, passive or active, that conditioned the ore shoot, saving only the original composition of the solutions that formed the shoot. Collection of data related to the shape and characteristics of veins should be followed by correlation of the data and the formulation of generalizations regarding ore formation. The nature of the criteria used in arriving at these generalizations is discussed. Certain of the criteria, when used with an understanding of their underlying causes, become "ore- guides." In the course of his study the geologist must not confine himself to the immediate surroundings of the veins, but should attempt to work out the geologic history of events culminating in the crucial epoch for any mining district, the period of mineralization. The work may involve study of features far removed from the veins and related to them only indirectly. It commonly means thorough study of the geology of the entire region surrounding the ore deposits. THE following question has been suggested for discussion: [t] "Are there any criteria by which one can determine when mining operations have reached the roots of an ore deposit?" The question deals less with the roots of a particular ore body than with the lower limit of the vertical range within which ore bodies may be expected. It concerns a critical line upon the longitudinal vertical projection of a vein.[t] Below this line it is useless to look for ore shoots; above the line exploration below the bottoms of individual ore shoots may be justified. Can we learn to determine the position of such a line? In some multivein districts the line for any given vein may be approximated by simple interpolation or extrapolation. Where this is possible the bottoms of the lowest ore shoots in the various veins are points on an imaginary, gently rolling surface. The trace of this surface upon the vein is our critical line for that vein. The imaginary surface rolls so gently that it may be projected from two or more known veins to an unexplored vein near by. Here is a criterion for the bottoming of ore that has nothing to do with changes in the appearance of the vein in question; it rests solely on the depth at which the ore bottomed in adjacent veins. The method is not applicable in districts only slightly explored in depth, nor where the lower limit of the ore-bearing horizons

Jan 1, 1939

By W. Denham Verschoyle

In designing a pocket instrumeut whereby any giver1 horizontal or vertical angle may be closely approximated, the following points should be kept in view, if general utility is aimed at : 1. The instrnment should be light and compact, so that it can be carried in the pocket, or in a sling. 2. It should be capable of observing any angle whatever, horizontal or vertical. 3. Since time is often an important consideration in making a preliminary survey, it should be capable of giving the horizontal and vertical angle at one observation. I do not know of any instrunlent that will fulfill these requirements, except the one here described. Where the depression- or elevation-angle of the distant object, whose bearing is required, exceeds 50 or 60 degrees, it becomes difficult or impossible with a prismatic compass, for instance, to obtain accurate results; and since it frequently happens, particularly in mining, that much work requires to be done beyond that limit, it is obvious that an instrument which can be used to observe a high angle just as easily as a low one, if not absolutely a necessity, will at least be a great convenience. How this a pocket transit" attains to the required degree of universality will be understood from the diagram, Fig. 1, in which B is a beveled, graduated circle, attached to and freely revolving about the center of the magnet A. Light falling on B is reflected through a window in F (the compass-box), along the line AC, and is again reflected back to the eye at D by the prism C. By a simple arrangement, the tight-line BCE call be completely revolved in the vertical plane DE, which is normal to AC. It is clear, then, that no matter through what vertical

Jan 1, 1908

By Jay A. Carpenter

This paper deals with only one step in the treatment of ore at the West End mill; not because the other steps are repetitions of practice in other mills, but because in this particular step there is in use the Trent agitator: This device, although it has apparently failed in many mills, is here giving excellent service and has proved to be well adapted for making a thorough replacement of pregnant solution with a minimum amount of barren solution. The strong and weak points of this agitator, its present simple construction, and its use as a thickener for agitator or battery pulp are features of interest; but perhaps the point of greatest interest to the metallurgist in this day of continuous decantation is its use in a series of tanks for slime treatment by the replacement method. The agitating department of the West End mill consists of six redwood tanks, 24 ft. in diameter, 18 ft. high, each equipped with a Trent agitator, a centrifugal pump, and a motor. The pulp is transferred by a pump from the top of a flat-bottomed tank to a set of arms and nozzles in the bottom of the tank, at just sufficient pressure to cause the arms to revolve. The streams from the many nozzles keep the bottom of the tank clean, and these streams, coupled with the effect of the revolving mechanism and the ascending current, keep the pulp in constant motion and of constant gravity. These agitating tanks hold 90 tons of dry slime and 202 tons of solution with a 1.24 pulp, our ore having a specific gravity of 2.7. This capacity is about 10 per cent. in excess of the standard 15 by 45 ft. Pachuca tank. The tanks are connected in one series for continuous agitation, the pulp for each agitator being drawn by its pump through a branch suction from near the top of the preceding tank and delivered to the bottom of the tank by the agitator arms along with the regular pulp of that agitator. This method works automatically, since the flow through the branch suction varies directly with the difference in head of the two tanks. The chance for new pulp to pass out quickly is, therefore, much less than in many other systems of continuous agitation, since the new

Jan 1, 1916

By Parke A. Dickey, R. Fettke

Drilling activity during 1944 increased considerably in the oil fields and slightly in the shallow gas fields of western Pennsylvania. The number of deep tests (middle Devonian or deeper) completed during 1944 was the same as in 1943 and did not result in discoveries of additional reserves of natural gas or oil. Thus far no commercial oil production has been obtained from sands below the Upper Devonian in Pennsylvania. As a result of the lack of new discoveries, oil production in nearly all of the producing areas in the entire Pennsylvania grade region declined 10 to 11 per cent. Stocks of Pennsylvania Oil The Peilnsylvania grade crude-oil stocks in storage on January 1943 were 2,479,000 bbl. In January 1944 crude stocks totaled 1,846,000 bbl., and during 1944 the stocks of Pennsylvania grade crude declined to a year-ending balance of 1,617,000 bbl. Nearly all of this oil is "unavailable for use," representing pipe-line fill, tank bottoms and limited working inventories at the refineries. The storage of Pennsylvania oil has declined to a point where little or no available crude oil is currently in storage. Prices The posted price of Pennsylvania oil remained constant during 1944; however, on Rug. I, 1944, the wartime Government subsidy was instituted at a rate of 75¢ per barrel. The average price in the Bradford area, including the subsidy, was $3.31 per barrel. New Technical Developments The Pennsylvania Grade Crude Oil Association started a rather ambitious program of research in production fundamentals and technology during 1944. Several well-qualified engineers have been employed and a laboratory is to be equipped at Bradford. The group will investigate, in cooperation with the American Petroleum Institute, the possibilities of bacteria as agents in oil recovery, and undertake other studies of both a fundamental and an applied nature. In cooperation with the Pennsylvania State College, the Research Group worked out a method of measuring water-intake rates in different strata. The method involves injecting salt water down a string of tubing and fresh water down the annulus, determining the location of the interface electrically, and measuring the input rates above and below the interface. The United States Bureau of Mines, in cooperation with oil companies of the Venango district, developed a simple gas-lift tubing string, which is operating successfully in some 20 wells. This device uses the air-gas mixture produced with the oil to lift it by the usual gas-lift principles. The Northern Ordnance Co. is experimenting with a chamber lift device that expels the oil in an unbroken column. These devices hold considerable promise

Jan 1, 1945

By Robert B. Kistler, Ward C. Smith

The borate industry is one of the few sectors of the mining and mineral-processing industry which the United States still dominates. Since about 1927, the United States has supplied over half of the world's total boron and borate raw materials, and many of the chemical derivatives as well. Chiefly responsible for this record are companies producing sodium borates from two large deposits in southern California, at Boron (Kramer) and Searles Lake. The sodium borates, or products derived from borax and borax-containing brines, are the preferred borates for industry because they are soluble in water and combine readily with most other chemicals. Calcium borates are required for certain end uses, and these are produced from smaller colemanite-ulexite-probertite bodies. Sodium-free borate compounds also are produced from boric acid, which can be manufactured from either sodium or nonsodium borate minerals. During the past hundred years, the use of boron compounds throughout the world has risen from a few tons per year to the equivalent of over a million tons of B2O3. Leadership in supplying borates shifted from country to country and from region to region during this period, generally as the result of the development of newly discovered deposits that were better in quality, more accessible, or more economically exploitable than previous sources (Table 1). Primary Products and End Uses The principal borate products offered by primary producers in the United States are listed in Table 2. In general, these products are utilized worldwide by almost all consumers, regardless of the original source of the primary borates, In the United States, the primary borates all originate in southern California. Colemanite is produced as crude or processed crude ore from the Death Valley area and is utilized by the fiber glass and ceramic industries without further treatment. Production from Searles Lake, CA is from brines that are processed in chemical plants where borax and other compounds are recovered and the principal borate products are produced. At Boron, CA, the world's leading producer is mining a deposit of mineral borax and operating a chemical refinery. The mineral borax is mined together with included clay, and refined borax or "10-mol" is one of the refinery products. The mineral and the chemical compound are identical, Na2B4O7 • 10H2O. In addition to ship¬ping all major refined borate products from [ ]

Jan 1, 1983

By J. A. M. van Liempt

SINCE the discovery, of von Laue, that a crystal forms a natural grating for X-rays, our knowledge of the structure of solids has gone forward with rapid strides. This progress is not only of purely scientific interest, but has also yielded direct technological results. One of the most valuable results is the broadening of our knowledge of the structure of pure metals and alloys. To promote these studies it is often desirable to have at our disposal pieces of metal consisting of one single crystal. As is so often the case in the natural sciences, we obtain the best results by making our earliest experiments on pure, simple materials and avoiding unnecessary complications. The Cryogen Laboratory at Leyden followed this method with much success, because the work was done at such low temperatures that the heat movement of the atoms was almost' absent. Similarly we can simplify the studies of metals by leaving out of consideration the influence of the grain boundaries and the mutual influence of the crystals by using unicrystalline instead of polycrystal-line metal. Methods of making single crystals have been scientifically studied during the past few years. Some methods were already known in the arts, but these have been improved and new methods have been developed. The methods for making metallic single crystals may be divided into the following groups: A. From the liquid state B. From the gaseous state C. Electrolytically D. By recrystallization in the solid state

Jan 1, 1927

The first discovery of gold in Montana is credited to François Finlay, a half-breed, from the Red River country, in Canada; he went to California during the early days and learned there how to wash the gold from placer deposits; then, on his return, he crossed Montana and found gold on the western slope of the Rocky Mountains, on Gold creek, a minor tributary of the Hell Gate river, in what is now Deer Lodge county. That was in 1852.* Finlay did not find enough gold to induce him to continue at work, but six years later a group of miners, led by the brothers James Stuart and Granville Stuart prospected on this same creek, obtaining about ten cents to the pan. They, however, were harassed by the Blackfeet Indians, and they were also handicapped by lack of proper tools; so they too desisted from further operations. Two years later, in 1860, Henry Thomas started to work on Gold creek with three sluice-boxes hewn out of green timber that he cut on the spot. With this simple apparatus he won from $1.50 to $2.00 per day. This may be considered the fist instance of systematic mining in Montana. Meanwhile the Stuarts went to Fort Bridger, in southwestern Wyoming, where they remained as traders until 1861, when, again lured by the gleam of gold, they returned to the valley of the Deer Lodge and resumed prospecting, using 10 sluice-boxes that were brought from Walla Walla, in Washington, 425 miles distant. In the summer of 1862 they were joined by many others, chiefly from Colorado, in consequence of an exchange of

Jan 1, 1932

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By Edgar Bain

OF THE important phenomenon of the hardening of steel, Professor Sauveur1 says: "It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem.. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say, this of other problems. It seems likely that one of the new avenues of approach to many metallographic problems is the study-of crystal structure, or more accurately, the atomic arrangement by means of the X-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of X-rays by Laue and the Braggs2 and later by Hull,3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the X-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 2, 1922

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By H. Leslie Bullock

From aluminum to zirconium, the quantitative preponderance of quartz as a gangue material is well recognized. lf this material is to be efficiently removed, its variations must be understood. Variations with temperature are especially important. Too little attention has been given to the thermal polarization of quartz. Under closely controlled conditions, electrostatic upgrading is very reliable. For efficient separation, contact charges must be fostered and charges due to radiation, surface coatings, or thermal polarization avoided. This paper lists thermal transition points of quartz and shows their effect on actual separations. Simple separation tests with all factors except temperature held constant are recommended for determining transition points. With silica making up more than 27% of the earth's crust, its oxides comprising more than 59% of all igneous rocks, and quartz accounting for most of the main free oxides, the mining engineer is in constant contact with quartz, which may occur as a valuable mineral to be purified or, far more frequently, as a gangue material to be removed as completely and economically as possible. As a means of effecting such purification or removal, dry beneficiation is becoming more and more desirable owing to local water scarcities, wet waste disposal problems, or freezing conditions. One method that has been gaining particularly rapid acceptance is electrostatic beneficiation, or the separation of dry free-flowing materials by means of opposite surface charges, differences in potential, or differences in conductivity. Electrostatic beneficiation dates back to the 1870's, but only in recent years have newly developed methods and apparatus and a growing knowledge of solid-state physics widened the field for its economical application. Because the term "electrostatic beneficiation" has been rather loosely used in the literature, it has come to include both electrostatic and electrodynamic procedures. Attracting type separators, however, in which oper- ation is based on differences of surface charge or potential, are truly electrostatic, because the separation occurs in a substantially static field set up between oppositely charged surfaces. Separations with this type of equipment may occur at potentials as low as 1000 v and seldom require potentials as high as 30,000 v. In the new contact charge dielectric separators1 the variation in charge is produced by continuous contact and separation of the particles in the moving feed stream and these charges are fostered by the use of non-conducting support and feed surfaces and by handling the feed in the form of streams of appreciable depth. This favors uniformity of feed and allows higher production rates. The distinctive surface charge differences are set up on the separation of the particles according to Coehn's Law,2 which states that equal and opposite charges are generated on the separation of any two materials in contact and that the substance having the highest dielectric constant will be positively charged. The basic contact charge concept is reliable, but all electrical charges are transient and modified by the electrical conditions of the surroundings. Pyro-electric, photoelectric and radiant effects may modify or totally destroy the contact charges necessary for efficient separation, or contact with conducting surfaces may neutralize them. Such hostile conditions must be carefully guarded against, since they have led to many costly failures in the past. The most consistent difference in surface charges to insure good separation is produced by repeated uniform contact and separation of particles in the moving stream. The thickness of the feed stream possible with this method reduces the effect of contact with the supporting surfaces, but as some contact is inevitable, the best results may be assured by having the dielectric constants of the supporting surfaces between the dielectric constants of the substances to be separated. In general, the hard smooth surface of quartz makes it an ideal substance for electrostatic separation from most minerals. For instance, with calcite, starting with a feed containing 1.9% acid insolubles, one can produce a concentrate containing 0.30% acid insolubles with a tailings containing 21.7% acid insolubles and a yield of 92.8%. The color can be held at 92 or above and the tint at 1.7 or lower. Working with specularite iron ore, laboratory work has given a concentrate of 68.8% Fe., with an iron unit recovery of 96.7%. Excellent results are also in pros-

Jan 1, 1969

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By P. D. Merica, J. R. Freeman, R. G. Waltenberg

Contents Page Constitution of Commercial Aluminum.................. 4 Solubility of CuAl2 in Aluminum at Different Temperatures........ 9 Effect of Magnesium on Solubility of CuA12 in Aluminum ......... 15 Solubility of Mg4Al8 in Aluminum at Different Temperatures........ 15 Solubility of Metals and Metal Compounds in Aluminum.......... 20 Summary and Conclusions......................20 Aluminum and its alloys have been the subject of much investigation1 during recent years, in the course of which the principal features of the constitution of most of the binary alloy systems with aluminum have been determined. Except in the case of a few metals—silicon, bismuth, cadmium, lead, zinc, and tin—an aluminum-rich compound is formed in each binary system, which forms a eutectic with the aluminum or its solid solution with this compound: Thus such compounds as FeAla, CuA12, Mg4Al3, and NiAls are formed, which are found in aluminum-rich alloys of their respective series as eutectics with the aluminum solid solution. These compounds are, in all cases, hard and brittle and their presence affects profoundly the physical properties of the alloys in which they occur. Within the zinc-aluminum system a compound, Al2Zn,, is formed that decomposes at lower temperatures. Silicon and tin each form a simple eutectiferous series with aluminum; bismuth, lead, and cadmium are only partly miscible in the liquid state with it. The extent of the solubility in aluminum, in solid solution, of these compounds or of the elements themselves, in the case of those series in which compounds are not formed, is of the greatest importance in

Jan 1, 1921

By Francis Foley

FROM the point of view of the metallographist, the adaptation of x-rays to the study of the crystal structure of metals is of the greatest importance. While one may hardly consider the findings resulting from x-ray study as revolutionary, their positive nature, compared with the deductions we have been forced to accept from the work that had gone before, gives firmer ground on which to build and furnishes new fields for speculation. Prior to the advent of the crystallogram, the best work on the crystal structure of steel was that of Osmond and Cartaud.1 They concluded, from their investigation with percussion figures formed at various temperatures, that alpha, beta, and gamma irons belonged to the cubic system and that they showed well-marked specific characteristics and could not have the same internal structure. What the internal structures were, they had no direct method of determining; but from a consideration. of the fact that the 001 plane (that parallel to the cube face) is a plane of perfect cleavage and minimum hardness in alpha iron and that the 111 (octahedral) plane is by far the most important in the crystallography of gamma iron, they were led to suggest the simple cubic arrangement as that of alpha and the face-centered cubic arrangement as that of gamma iron. They suggested the body-centered cubic arrangement as that of beta iron. The atomic arrangement of the various crystal forms of iron has been quite definitely determined in recent years by means of x-rays and the work of Westgren2 and Westgren and Phragmèn3 has been rather conclusive. They not only determined the atomic arrangement of alpha, beta, and gamma iron but also that of the high-temperature modification delta.

Jan 10, 1925

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923