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By Hobart M. Kraner

THE mineralogy of blast furnace sinter is of interest because its mineral content is one of the important factors contributing to its character. There are so many other factors affecting the properties of the sinter, however, that it is well to mention them here. The proportion and character of the raw materials, that is, raw ores, concentrates, returns, and fuel, as well as the mixing and the water content, all have a marked effect on the physical properties of the product and the degree to which sintering action can be carried on. The process of sintering is a relatively fast operation. In as much as appreciable time is required to carry on processes of fusion in such masses of low thermal conductivity, large lumps of hematite ore frequently remain unfused and partly unchanged in state of oxidation in the sintering process. The kind, the grain size, and the amount of fuel used affect both the completeness of the fluxing reaction and the prevailing atmosphere. The rate of reduction in laboratory tests is not only dependent upon the state of oxidation of the sinter but also upon the sizing and porosity.

Jan 11, 1953

By C. Wert, P. Bunn

Determination of the solid solubility of gases in metals is usually done by one of two methods. The first is an additive method, in which measurement is made at temperature of the maximum amount of gas absorbed by an initially degassed piece of the metal. Gas additions are made until the dissolved gas first comes into equilibrium with a compound. This method is most useful at relatively high temperatures where the amount of gas absorbed is relatively large and where equilibration of the dissolved gas with the gas atmosphere can be achieved in a relatively short time. The second is a precipitation method. A supersaturated solution of the gas in the metal is held at temperature until equilibrium is established between the gas atoms in solution and a compound. The quantity of dissolved gas is then determined by some physical measurement which is sensitive only to the gas in solution. This method is generally useful in low temperatures. This paper describes measurement of solubility of nitrogen in tantalum whereby measurements at low temperatures using internal-friction methods are plotted together with existing measurements at high temperatures. The solubility is thereby known from less than 0.5 at. pet at 350°C to near 13 pet at 2300°C. Several measurements have been reported of the solubility of nitrogen in tantalum. These are collected in Fig. 1. Three single determinations by Ke,1 Andrews,2 and Brauer and zapp3 are plotted along with a series of measurements by Vaughn, Stewart and schwartz4 and Gebhardt, Seghezzi, and Fromm.5 Although not much doubt exists about the solubility being in excess of 10 at. pet above 2000°C, the solubility indicated at low temperatures depends on whose data are selected as being most reliable. The variation is enormous, being at least an order of magnitude at 500°C. Accordingly, a measurement was begun to examine this discrepancy. The method of measurement finally selected was that of internal friction. A solid solution of nitrogen in tantalum was prepared by heating a tantalum wire in a dilute at-

Jan 1, 1964

By R. E. Johnson, J. W. Donaldson, D. B. George

Accurately predicting the minor element content of an anode product is an important part of an evaluation of copper smelting processes. A general review of the minor element behavior in copper smelting is presented with the techniques to predict anode quality as a function of important process variables. Among variables considered are concentrate composition; recycle of dust, sludges and other intermediate byproducts from smelters and refineries; and other important smelting variables, including matte grade and the slag cleaning process. To evaluate the complex nature of minor element behavior relative to these variables, special techniques have been developed and are described.

Jan 1, 1976

By W. A. LaVenue, W. M. Houston

Pebble phosphate mines of Florida have been established from south of Hardee County to north of the Georgia state line, a distance of over 200 miles. Mining has been carried out on an ever-increasing scale since 1885, but phosphate deposits that can be mined on the economical standards of today, are confined in a roughly circular area about 30 miles in diameter, generally within Polk and Hillsborough Counties, in the central part of the State. The phosphate deposit, which is in the Bone Valley formation of Pliocene age, is covered by Pleistocene terrace deposits of unconsolidated quartz sand. The matrix is composed of approximately 1/3 clay slimes, 1/3 silica sand and 1/3 phosphate pebbles. The phosphate usually occurs as rounded pebbles, ranging in size from about 1 in. down to approximately 400 mesh. The phosphate may vary from well-defined hard pebbles to soft weathered rock. The color and character of the phosphate will range from smooth buff pebbles to black and white "salt-and- pepper rock." The screen size distribution varies considerably between locations; the recoverable phosphate may extend down to the 400-mesh size in some areas, while in others the phosphate may cut off sharply at about 35 mesh.

Jan 11, 1962

The Free World's largest uranium reserves are in the United States. Almost 97% of the U.S. uranium reserves occur in irregular shaped sandstone formations, widely disseminated in coarse clastic sediments that are mostly of Jurassic or Tertiary age. Without doubt, the most important deposits are located in the sandstone formations of the Ambrosia Lake district of New Mexico, near the sun-scorched town of Grantswhose proud alias, as given by the city fathers, is "The Uranium Capital of the World."

Jan 8, 1974

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By R. D. Daniels, T. W. Wood

The tensile properties of columbium and Cb-H alloys containing up to 455 ppm H were studied as a function of temperature and strain rate. Hydrogen, introduced into columbium at elevated temperatures, using a thermal -equilibrium technique, embrittled columbium most severely at about —77°C. This elnbrittle ment occurred even at hydrogen concentrations of an order of 20 ppm. At higher temperatures, the hydrogen tolerance of columbium increased in relation to the increased solubility of hydrogen in tile metal. Below this temperature hydrogen tolerance, as determined by ductility and fracture stress, increased slightly. Strain rate had little effect on the tensile results for cross-head speeds over the range 0.002 to 2.0 in. per min. Strain aging during the tensile test appears to explain the ductility mininmum at —77°C. The apparent increase in hydrogen tolerance at lower temperatures is attributed to the low mobility of hyhogen. Experiments were performed in which samples were prestrained in tension at room temperature and tested to failure at —196°C. Results suggest that hydrogetz segregation to preformed crack nuclei can cause subsequent embrittlement even at temperatures where hydrogen mobility is too low to cause embrittlement in a normal tensile test. COLUMBIUM is an example of the class of bcc metals with ductile-brittle transition temperatures sensitive to the presence of interstitial atom contaminants. Hydrogen is one of these embrittling contaminants. The embrittling effect of hydrogen is less potent, perhaps, in columbium than in some of the other bcc refractory metals, but it is still a problem of both theoretical and practical interest. Unlike hydrogen in iron and steels, hydrogen in columbium is exothermically rather than endo-thermically occluded. The embrittlement process in exothermic systems has not been studied as extensively as that in endothermic systems, especially at hydrogen concentrations below the limit of solubility. The purpose of this investigation was to evaluate the embrittlement process in initially pure columbium as a function of hydrogen content, temperature, and strain rate. The Cb-H phase diagram, according to Albrecht et al.,1 is shown in Fig. 1. Columbium reacts exothermically with hydrogen producing a solid solution at concentrations of less than about 250 ppm (parts per million by weight) H at room temperature. At concentrations above the highly temperature-dependent solvus a second phase is formed. Like many similar hydrogen-metal systems,2 his system exhibits a miscibility gap with respect to hydrogen solution. Albrecht found the critical temperature of the miscibility gap to be about 140°C, the critical concentration to be 0.23 atom fraction hydrogen, and the critical pressure to be 0.01 mm Hg. Above 140°C there is a solid solution of increasing lattice constant extending across the phase diagram. Hydrogen concentrations of particular interest in this investigation were those below the limit of solubility in columbium. At hydrogen concentrations above the limit of solubility, columbium will contain the hydrogen-rich second phase and will be brittle under most testing conditions because the hydride generally precipitates as platelets with coincident matrix lattice strains.1'3 At hydrogen concentrations below the limit of solubility, the tensile behavior of columbium is expected to be more sensitive to the interrelationships between hydrogen concentration and mobility and the testing variables such as temperature and strain rate. Literature references to the hydrogen embrittlement of metals, especially ferrous alloys and titanium alloys, are too voluminous to mention. It is only recently, however, that detailed studies of the hydrogen embrittlement of columbium have been undertaken. Wilcox et a1.4 studied the strain rate and temperature dependences of the low-temperature deformation behavior of fine-grained are-melted columbium (1 ppm H) and the effect of hydrogen content (1,9, and 30 ppm H) on the mechanical behavior of columbium at a series of temperatures for a single strain rate. A strain-aging peak was ob-served at about -50°C which was attributed to the presence of hydrogen in the metal. Eustice and carlson5 studied the effect of hydrogen on the ductility of V-Cb alloys at a series of temperatures over the range -196° to 25°C. Pure columbium was embrittled by 20 ppm H which produced a ductility transition at approximately -70°C. Ingram et al.6 studied the effect of oxygen and hydrogen on the tensile properties of columbium and tantalum. A minimum in the notched-to-unnotched tensile ratio of hydrogenated columbium was obtained at about -75°C, but because of the relatively large hydrogen content employed (200 and 390 ppm) the ductility

Jan 1, 1965

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

By C. D. Hunter, J. B. Browning

During the year 1934, Kentucky oil and gas operators have partly overcome their past depression fears and in the oil industry, with possibly more abandonments of old oil producers than the completion of new oil wells, produced 4,814,904 bbl. of oil in 1934 against 4,501,511 bbl. in 1933. In the gas industry of eastern Kentucky, 115 gas wells were completed during 1934. This production is delivered through two 20-in., one 16-in., one 12-in., one 10-in., and two 8-in. pipe lines to supply both domestic and industrial markets in Cincinnati, Ohio; Louisville, Lexington, Frankfort, Winchester, Ashland, Covington and other Kentucky towns; Washington, D.C., and other eastern cities. The largest percentage of these gas wells and production are from the Devonian black shale area of Floyd, Pike, Knott, Martin and Magoffin counties, Kentucky. In this area the largest percentage of 1889 wells, developing 421,-215 acres, has been completed in the past 10 years, of which 55.3 per cent produce from the 400 to 550 ft. of Carbonaceous Devonian black shales. The successful results obtained from these Devonian shales are due to the physical effects of the 5000 to 6000 lb. of gelatinated nitroglycerin with which the entire 400 to 550 ft. of shale is shot. A very small number of the shale wells are natural producers and do not require shooting. Other than the Devonian shale gas production, the remaining 44.5 per cent of the gas in this field is encountered throughout the entire strati-graphic section above this horizon; namely, salt sands of Pennsylvanian age and Maxon, Big Lime and Weir of Mississippian Age. A very small percentage is encountered in the Corniferous Devonian lime and the Silurian Big 6 below the black shales. In western Kentucky, in the counties of Henderson, Webster, Hopkins, McLean, Christian, Muhlenburg, Ohio, Daviess, Hancock, Brecken-ridge, Hart, Barren and Warren, many gas wells have been completed, but, because of insufficient market, activity has been somewhat desultory. The area is served by the pipe lilies of the Kentucky Natural Gas Corporation, with headquarters at Owensboro. Their market is increasing and the gas is delivered to Owensboro, Henderson, Madisonville, and many

Jan 1, 1935

By P. de Vitry, Oliver Bowles

THE conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 3/1 6 or 1/4 in. The equipment, methods used, and accomplishments have been described in previous reports.1-7 Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible. to maintain in stock marbles of the color, size, and thickness called for,, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill. such, orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the [ ] twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with

Jan 1, 1941

By J. M. Toguri, H. Flood

The application of the mass action law to the thermodynamic treatment of metal-slag equilibria is discussed. The consideration of the reactions essentially as ionic exchange equilibria is shown to be both an advantage and an aid for the elucidation of the theoretical treatment. This is illustrated by several examples. In general two different methods of application of the mass action law to metal-slag equilibria have been used by different groups of investigators. These could be called the oxide reaction and the ionic reaction approach respectively. At the recent discussion in the metallurgical section of the I.U.P.A.C. Congress in Montreal, 1961,' divergent opinions prevailed regarding the most rational way of applying the mass action law to metal-slag equilibria. This question is of fundamental importance in the treatment and understanding of theoretical chemical metallurgy. Consequently, the following is an attempt to contribute towards its clarification. As an example, the distribution of iron and manganese between molten iron and slag will be considered. I) THE OXIDE EXCHANGE REACTION APPROACH The equilibrium between iron and manganese between molten iron and slag is frequently formulated as an oxide metal exchange reaction as follows:

Jan 1, 1963

By Charles S. Barrett

THIS paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstructures. About 12m exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,1 and a number of these have been selected to illustrate the results obtained. Prints are also included showing the common types of falsities-to borrow a term from the biological field, the "artifacts." In brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. n addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains. Since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. SPECIMEN PREPARATION AND PHOTOGRAPHS Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for repeated polishing and etching (each successive polish becoming less severe and each etch lighter), since the final etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and IC, the replicas used were of silica, deposited up0n polystyrene and floated from the polystyrene in ethyl bromide according to polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1943

By C. E. Webber

THE economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro-carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,5 who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40° to 200°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33° to 180°F. and from 100 to 5000 lb. per sq. inch.

Jan 1, 1940

By A. U. Seybolt

The solubility of oxygen in a iron has been determined in the range between 700° and 900°C. The solubility is a function of temperature and varies from about 0.008 pct oxygen at 700°C to atureandabout 0.03 pct at 900°C. The heat of solution is approximately +15,500 cal per mol. AS pointed out in a recent paper by Kitchener et al.,1 there has been a lack of agreement among many investigators even as to the order of magnitude of the solid solubility of oxygen in the various forms of iron. This lack of agreement is attributable in large part to the difficulties in the determination of a small oxygen solubility; but because the problem has remained so long unsettled, it also indicates a lack of interest which is rather surprising when the demonstrated importance of small amounts of soluble nonmetallic impurities in iron is considered. The work of Kitchener et al. apparently leaves the solubility of oxygen in iron in a satisfactory state, but no attempt was made to investigate the solubility in a iron. The solubility of oxygen in a iron is actually of greater interest, since it is in this form that iron and mild steels are employed ordinarily. That the effect of oxygen in iron is of more than theoretical interest has been well established by Fast,' and more recently by Rees and Hopkins," who demonstrated that oxygen in the range between 0.0008 and 0.27 wt pct has a pronounced effect upon the mechanical properties. Previous Work and Methods Used To report in detail the literature relating to the solubility of oxygen in a iron would require an inordinate amount of space. For those interested in reviewing this work, a bibliography4-13 of the more significant papers is appended. In general, two methods of studying this problem have been used. One is the gas-metal equilibrium method where the H2O-H2-Fe or the CO2-CO-Fe equilibria have been used. The other is the more direct approach of the oxidation of thin strips of pure iron by packing in mill scale or by air or gaseous oxygen at some desired temperature. In this method oxygen is allowed to oxidize the surface and then to diffuse inward until saturation is obtained. In the gas-metal equilibrium method the oxygen dissolved in solid iron at a given temperature is proportional to the ratio of the water vapor-hydrogen pressures or the CO2-CO pressures over the sample for small ratio values. If the ratio becomes higher than a critical value, then an oxide phase makes its appearance (the solution becomes supersaturated). In principle, it is possible to use a series of H2O/H2 or CO2/CO ratios and to find by analysis the corresponding amounts of oxygen in solid solution at constant temperature. At the point where a very small increase in the gas ratio (increase in oxidizing powder) produces a large increase in oxygen content, the solid solubility limit is reached. Alternately, if the critical ratio is known, it is possible to use the procedure of Kitchener et al.1 and to use a ratio which is near but below the critical one. The solubility corresponding to this lower ratio will not be the saturation solubility at the temperature employed, but the saturation solubility can be calculated by multiplying the measured solubility by the critical ratio over the ratio used. However, in the case where oxygen gas is the oxidizing medium, the saturation solubility is not a function of pressure, providing the pressure exceeds the dissociation pressure of FeO in equilibrium with iron. This is 1.2x10-16 mm at 800 °C, according to Dushman." As pointed out by Darken17 in discussing the FeO phase diagram, most of the possible errors tend to yield high values of oxygen solubility. For example, one circumstance which evidently caused the reporting of many high values was the use of finely divided or powdered iron in the gas equilibrium method. Because of the large surface area of such a sample, and the likelihood of some surface contamination if only by exposure to air, the results tended to be high. The direct oxidation method which was used in this work has the advantage in that it is simple and direct, but it suffers from one disadvantage: equilibrium can only be approached from the low oxygen side. The important factors to be kept under control are the following: 1—use of high purity iron to avoid internal oxidation (oxidation of readily

Jan 1, 1955

By D. Hanson

Fox most of their practical applications metals are required to with-stand stresses of appreciable magnitude: indeed, it is because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances-or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By H. J. Morel-Seytoux

Methods of predicting the influence of pattern geometry and mobility ratio on water flooding recovery predictions are discussed. Two methods of calculation are used separately or concurrently. The analytical method yields exact solutions in a convenient form for a unit mobility ratio piston-like displacement. A few typical pressure distributions, sweep efficiencies and oil recoveries are presented for various patterns. For non-unit mobility ratio, one may resort to a numerical method, such as that of Sheldon and Douherty. 1,2 Because the domains of applicability of the analytical and numerical techniques overlap, the exact solutions provide estimates of the errors in the numerical procedures. The advantages of the analytical and numerical methods can be combined. To develop a numerical technique as independent of geometry as possible, the physical space is transformed into a standard rectangle. The entire effect of geometry is rendered through one term, the "scale-factor", derived from mapping relations. The scale factor can be calcu-lated from the exact unit-mobility ratio solution for the particular pattern of interest. By this means recovery performances for arbitrary mobility ratio con be obtained for many patterns. A sample of tesults obtained in this manner is presented. INTRODUCTION Pattern geometry and mobility ratio are two major factors in making a waterflood recovery prediction. Because assisted recovery has become increasingly important to the oil industry, pattern configuration and mobility ratio also assume a greater significance in the assessment of the economic value of recovery projects. The influence of pattern geometry and mobility ratio in shaping a recovery curve and on the other quantities of interest to the reservoir engineer is the main subject of this paper. Much effort has already been spent on estimating quantitatively the influence of either pattern or mobility ratio or both on oil recovery. The literature reports many investigations of this nature. 3-9 However, many results or methods of recovery prediction presented in the literature cannot be considered fully satisfactory. Even for unit mobility ratio and piston-like displacement, where analytical solutions are available, the literature shows discrepancies. For non-unit mobility ratio, the divergence in the results is extreme. For infinite mobility ratio in a repeated five-spot, depending on the investigator, the sweep efficiency ranges from 0 per cent to 60 per cent. With respect to the influence of pattern on recovery, only the repeated five-spot has received much attention. Other confined patterns and pilot configurations have received very little attention. Two calculation methods are presented in this paper, either separately or concurrently: the analytical method of potential theory and the numerical method of finite-difference approximation. The analytical method is more restricted in scope than the finite-difference method, but it has the definite advantage of providing exact solutions within its range of applicability. If a unit-mobility ratio piston-like displacement is assumed, the analytical approach is possible. A few typical results are reported in this paper; the detailed description of the general method and of a great variety of results will be the subject of other articles. Fornon-unity mobility ratio, we must resort to a numerical scheme. The numerical technique is that which was described by Sheldon and Dougherty.l,2 It is not limited to piston-like displacement. However, mainly single interface results will be presented here. Because the respective domains of applicability of the analytical and the numerical method overlap, useful comparisons of exact and numerical solutions can be made for a variety of patterns. The advantages of the analytical and numerical approaches can be combined. The reason for the success of this analytical-numerical approach can be summarized in the following two points: 1. The numerical solution for arbitrary mobility ratio can be programmed most efficiently when the physical space in which the displacement actually takes place is transformed into a standard shape; and 2. This can be done with remarkable simplicity whenever an analytical expression for the pressure

Jan 1, 1966

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By Y. C. Liu, G. A. Alers

Using X-ray pole-figure information and the single-crystal elastic constants, the angular variation of an elastic modulus in a polycrystal can be calculated and compared to measured clalues. This procedure has been used in the past to provide supporting ecidence for a particular choice of ideal orientations in the description o the X-ray pole figure. Since it is well-known that the absolute value oj an elastic modlus oj a poly crystal cannot be acczrralely calculated from the single-crystal elastic constants, there exists a serious question about the reliability oj this modulus method in the study of textures. This paper deriz-es sez3eral simple fornzulae for the ntzgular lariatiion of Young's modulus in the plane o a rolled sheet sing the same ssuinptions which lead to the lack oj detinztion of the absolute c'alre OJ the elastic ,nodulus. The vesults show that, although the absolute isallre oj Young's modulus depends strongly on the assumptions made, the shape of the modulus vs angle curve is not very sensitive to the assumptions and thus can be used reliably in texture studies. Exatzples oj' using this criteriotz are illustrated in the text. NeARLY all poly crystalline materials have some preferred orientation in the arrangement of their grains and hence exhibit anisotropy in their properties. This preferred orientation is usually measured and studied by X-rays which yield detailed information on the statistical distribution of grain orientations in the form of pole figures. The usefulness of these pole figures in theories of texture formation and in predictions of properties has come to depend almost entirely on the characterization of the pole figure by one or more ideal orientations. Unfortunately, this characterization is not unique and different authors often present different ideal orientations to characterize a given pole figure. In order to distinguish between these different choices of ideal orientations, it is necessary to go beyond X-rays and consider other physical properties which reflect the texture' simply because any choice of ideal orientations must predict correctly the observed anisotropy in all physical properties. The most common example of this procedure has made use of the angular variation of Young's modulus with respect to the rolling direction in the plane of a rolled sheet.3 4 Here the anisotropy can be measured easily and it can also be calculated from the single-crystal elastic constants and the chosen ideal orientation. Unfortunately the methods used to calculate this anisotropy were chosen for their simplicity rather than for their mathematical rigor so that there exists a serious question as to the validity of conclusions reached by this modulus method. It is well-known5 that the absolute value of the Young's modulus of a polycrystalline aggregate cannot be calculated very accurately because different mathematical averages over the grains yield different results. It is one purpose of this paper to examine the effect of different averaging procedures on the calculated anisotropy of Young's modulus in the rolling plane of rolled sheets in order to see if this property can be used reliably in texture studies. This particular modulus and type of material were chosen because the modulus is easily measured and rolled sheet is technologically important. The results show that, although different averages yield different absolute values for Young's modulus, the shape of the modulus vs angle curve is not very sensitive to the averaging procedure and thus can be used as a criterion to check the various ideal orientations used to characterize the X-ray pole figure. Examples of this checking procedure are given in the final section. Another purpose of this paper is to examine the possibility of using the anisotropy of Young's modulus as an indicator of texture without reference to pole figures or ideal orientations. Such a use would require that different textures yield quite different shapes for the modulus vs angle curve so that the distinction between textures would be quite clear. The experimental results presented in the final section indicate that there is easily enough variation in shapes to allow modulus measurements to be useful texture indicators, par-

Jan 1, 1967

By J. E. Tobey

UNDER war conditions coal immediately assumes a position of highest importance for coal must carry the basic load for industry. The upward trend in production continued through 1941. Bituminous coal production alone about equaled the total output of bituminous and anthracite in 1940. The figures for 1941 approximated 500,000,000 tons for bituminous, and 54,000,000 tons for anthracite, and production of by-product and beehive coke exceeded that of the previous year. The coal industry, under the National Bituminous Coal Act, is going through a period of readjustment, and is beginning to stabilize itself under the statute. The Federal Mine Inspection Nill became law during the year.

Jan 1, 1942

By G. F. Fix

Oil and gas activity reached a higher peak in Indiana during 1940 than for any like period during the past decade. Major activity, as during 1939, was in the southwestern part of the state, the Indiana portion of the Eastern Interior Coal Basin, where most of the increase was due to field drilling in previously proven areas. The amount of wildcat drilling was about the same as for 1939. No new fields of any apparent consequence were discovered during the year, with the possible exception of the College pool, in southwest Posey County. Only one well had been completed in this area at the end of the year. About 10 ft. of saturated Aux Vases sandstone was drilled in this well and the initial production was I00 bbl. of oil a day. Other discoveries during the year 1940 include: St. Thomas, in southwestern Knox County, where four McClosky wells, ranging from I00 to 300 bbl. a day initially, were com-pleted; Buff kin, in central Posey County, with 11 oil wells and 5 gas wells completed; and new developments in two old areas —Randolph County (part of the old Trenton field) and Gentryville, northwestern Spencer County, where some oil was found many years ago. The St. Thomas field proved disappoint-ing, with very spotty production from the McClosky horizon of the St. Genevieve limestone at a depth of about 1875 ft. The discovery well flowed 362 bbl. a day ini-tially. At the end of the year the field was pretty well outlined by dry holes and some inside locations were dry. The Buffkin pool also proved spotty, with production from shallow Pennsylvanian sands and from the Basal Pennsylvanian Mansfield sandstone, the latter at a depth of approximately I175 ft., with small production from the Cypress sandstone of Chester age. Oil wells in this pool are small, ranging from 25 to 75 bbl. a day. The Randolph County area, on the east side of the Trenton gas field, showed some promise for a commercial gas field, with four completed gas wells having cumulative initial flows of about 1,200,ooo cu. ft. a day. The area appar-ently was not depleted during the Trenton boom at the turn of the century, since casing pressures are about as high as the virgin pressure in the old field. Elsewhere the pressure has dropped as low as 5 pounds. The Griffin field received most of the drilling during 1940, with 163 completed oil wells. This field now covers about 3200 acres on the Indiana side of the Wabash River and is not as yet completely delimited. It produced the major part of Indiana's oil during the year—a total of 3,594,000 bbl. At the end of 1940, there were 253 producing wells in Griffin. New Harmony had five completions for a total of 24. The Rockport field, in Spencer County, continued to be actively developed and had a total of 45 gas wells and 9 oil wells at the end of the year. Oil in commercial quantities had not been found in the field previous to 1940. Total gas production for the year was 394,470,000 cubic feet. In all, 521 wells were drilled in the state during 1940, as compared to 377 for 1939. Of this number 248 were oil wells, 77 were gas wells and 196 were dry. Divided into

Jan 1, 1941