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By P.V. Roundy, G.R. Mansfield

Public lands in Florida were first withdrawn from entry by President Taft on July 2, 1910, as a conservation measure because of their possible phosphate content. The reserve thus established was subsequently modified by further withdrawals and by restorations, so that on Jan. 1, 1934, it contained 66,796 acres, of which only a small part had been definitely classified. The reserved land was in scattered parcels, ranging from less than 40 acres to 320 or more, distributed in many counties. For administrative purposes and for final disposal of any of the numerous parcels, mineral classification of the land is legally necessary. In 1934 and 1935 the United States Geological Survey, under two successive grants from the Public Works Administration, prospected some 83 tracts of these lands in Polk County, comprising in all about 3300 acres, and six tracts comprising 240 acres in Citrus and Marion Counties. The tracts in Polk County were all in the so-called land-pebble field and the others in the hard-rock field. The Survey field party was under the direction of P. V. Roundy, from whose unpublished report the material in this paper is largely taken. The foreman of the prospecting crew was J. H. Wingate of Zephyrhills, Fla. The individual tracts were identified through the cooperation of the General Land Office, by transitman Hugh B. Crawford. This prospecting work fitted well the classification adopted for Public Works projects in general: it could not be done on any considerable scale under the Survey's usual appropriations; it gave employment to unemployed labor; and it may be expected ultimately to repay the Government in royalties more than the cost of the exploration. Commercial, Prospecting Methods Commercial methods of prospeeting for phosphate in Florida have been briefly described by Mansfield.' In the hard-rock field, where the floor of the phosphate deposit is extremely irregular, it is customary to drill a.:

Jan 1, 1938

By George Sachs

I deeply appreciate the honor of being selected to deliver the twentieth Annual Lecture of the Institute of Metals Division. The subject of my paper is extremely involved and voluminous, therefore I shall discuss only some more recent experimental material and speculate somewhat on the physical and mechanical fundamentals of these changes. The flow and the rupture of a solid material are rather different phenomena. It is therefore surprising that up to a rather advanced stage in metallurgical science these two fundamental phenomena have been simultaneously treated and forced into the general conception of the "failure " of solid material. Only in this century, and particularly during the last 20 years, have the very different physical meanings of flow and rupture been clearly recognized. Several hundred of the more recent publications deal with these subjects.l Law of Similarity The basic values commonly considered responsible for the mechanical behavior of any material are the stresses. From this standpoint both a large and a small article made from the same homogeneous metal and of geometrically similar shapes should behave identically, i.e., they should deform geometrically in a similar manner, if subjected to the same stress values at corresponding points. This "law of similarity" was introduced about 60 years ago simul- taneously by Barba2 and Kick3 and was derived from the classical theory of elasticity. As far as the plastic behavior of a metal is concerned, this rule appears to be valid. The conventional properties of large and small tension or compression test bars, machined from larger sections, are identical; while the force required to deform a section is proportional to its cross-sectional area and the work consumed in deforming geometrically similar articles in a geometrically similar manner is proportional to its volume. The general trend of the stress-strain diagram of a metal is independent of the section size (Fig. I). No exceptions from this rule are known. However, if the deformation of a metal is continued until rupture occurs, and the breaking stress or the work consumed is measured, a test bar of large cross section appears to fail before or at lower stresses than does one having a small cross section. Thus, the specific impact energy has been often found to decrease with increasing size of the test specimen, particularly for materials with a limited ductility.4 Another exception from the rule of similarity is offered by fatigue-strength values, which usually decrease with increasing section size.6'6 The conclusion must be drawn from these experimental facts that the ductility of a homogeneous metal decreases with increasing section size (Fig. I). This effect has been actually confirmed by Docherty,7 who observed that in static notch bending tests large specimens failed earlier and in a more brittle fashion than small specimens ma-

Jan 1, 1941

By R. M. Brick

The etched mierostructures of cold-worked alpha brasses, after reductions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonymously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {ill), in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson6 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into symmetry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By B. H. Sage, W. N. Lacey

An apparatus is described for the measurement of the pressure-volume-temperature relations of pure substances, simple mixtures and complex mixtures with an over-all absolute uncertainty, which is usually not more than 0.2 per cent. The equipment is suitable for studies in the gaseous, two-phase, and liquid regions. The behavior of such systems may be investigated at pressures as high as 10,000 lb. per sq. in. for temperatures between 70 and 600 F. The methods of measurement and the construction of the apparatus are described in some detail. The measurement of the volumetric behavior of multicomponent systems requires the simultaneous measurement of the pressure, volume, temperature and weight of each component of the system. In the present apparatus a sample having constant weight is investigated at a number of independently controlled pressures and temperatures, therefore it is necessary only to establish the weight of each component added before a given set of measurements. This method is in distinction to that in which the total volume remains constant and the pressure is varied by addition or removal of material, the system having variable weight. An objective in the design of the apparatus to be described was to develop equipment that would yield results involving no uncertainties larger than 0.25 per cent throughout the range of pressures from 150 to 10,000 Ib. per sq. in. at temperatures between 70" and 600" F. Although this over-all absolute uncertainty of measurement may not appear to be small, it necessitated care in the plans for control and measurement of each of the fundamental variables. In general, any uncertainty greater than 0.05 per cent in the pressure, volume, absolute temperature or weight of each component was considered undesirable; therefore the attempt was made to obtain a precision of measurement in each case such that the absolute uncertainty would be only half this amount except in certain regions near the ends of the experimental range of the variable under consideration.

Jan 1, 1940

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Frederick N. Rhines

Because of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding their occurrellce, even though the fundamental mechanisms invalved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by Processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpiet the next. It is the purpose of the present Paper to present, by means of examples drawn from practice, a brief survey of the ways in which gas-metal diffusion serves and obstructs the Purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with ' but brief mention of parallel cases. The Nature of Gas-metal Diffusion The term ugas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of " substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain.temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. NO element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By R. F. Miller, R. F. Campbell

Sixteen steels containing different combinations of chromium and molybdenum, in amounts up to 5 per cent of each element, were examined for microstructure and hardness after air cooling and after furnace cooling from suitable austenitizing temper- atures. Diagrams summarizing the structnres and hadness resulting from these two cooling rates are presented (Figs. 3, 4, 7).t Data were also obtained on the influence of these two elements, individually and in combination, on the depth of decarburiza-tion observed after furnace cooling (Fig. 8). Composition of Material The chemical composition of the steels investigated is given in Table I. The plain carbon steel was made in a 2 5-ton Heroult electric-are furnace, while the alloy steels were made in a 4.5-ton Ajax-Northrup elec- tric induction furnace. The cast ingots were hot-rolled to 1.75-in. bars. Air-cooled Series The I.75-in. bars were forged to flat plates, 0.25 in. thick, from which specimens 0.5 in. wide by 2 in. long were cut. The specimens were pretreated to improve their homogeneity by heating to 1830°F. (I000°C.) for 20 min. and oil-quenching. They were then reheated to 1740°F. (950°C.) for one hour and air-cooled, after

Jan 1, 1942

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By T. R. Graham, R. G. Feustel, J. R. Long, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By Holbrook G. Botset

It is possible by means of the electrolytic model to simulate water-flooding or gas recycling systems involving input and output wells, and also the encroachment of a natural water drive. The results are obtained pic-torially, and by simple measurements and calculations the percentage of recovery is obtained qualitatively as a function of the total input. Introduction The increased demand for petroleum products, together with the decline in discovery rate and the higher cost of recovery as deeper formations are brought into production, has stimulated interest in methods for studying and predicting efficiencies of various production programs. Among methods Of recovery that have become of increased significance recently are gas recycling in condensate fields and secondary recovery by water-flooding. The electrolytic model is a useful device for studying such methods in the laboratory, at least in a qualitative way. The original experiments with electrolytic models and the development of their application to the study of secondary reCoverY problems were published in 1933. 1,2,3 Subsequently other investigators continued the development and modification of the bait method, with resultant improvements and extension of its applications.4-7 The method and equipment to be described here are thought to represent still further improvement in the results obtainable, with increased validity in their application to field problems. Sand OF Principles of Operation The underlying theory of the operation of the model is given in references I, 2 and 3. However, a brief statement of principles involved is given herewith. The applicability of the model is based on the fact that Ohm's law and d'Arcy's law are exactly analogous; whence, electrical flow through a conducting medium may be used to simulate homogeneous fluid flow through a permeable medium. If two electrodes are placed in a conducting (ionized) solution and connected to the positive and negative terminals of a source of direct current, the positive ions of the solution will move toward the negative terminal, Since the velocity of an ion in an electrolytic medium is proportional to the electrical gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the motion of the ions in the potential field will be the same as the motion of fluid particles in a porous medium if the positive and negative terminals (input and output wells) and boundary conditions are made equivalent in shape and distribution. In order for the analogy to hold exactly, the sand must be assumed to have uniform porosity and permeability and the input

Jan 1, 1946

By Thomas C. Wilder

The concentration and activity of oxygen in liquid copper has been measured by the reversible galvanic cell: at 1100°and 1200°C for the concentration range of oxygen of 3 to 5600 ppm Measurements for approximately thirly alloys at each temperature indicate that the activity of oxygen roughly follows Henry's law, the activity coefficients of oxygen being 0.12 and 0.205 at 1100° and 1200°C, respectively. These results compare javorably with the results of seven other electrochemical and gaseous equilibrium studies on this system, the free energy of the solution reaction 1/2 O2 = O (7 at. pct in Cu, liq) being -18.10 * 0.30 kcal per gfw at 1200°C. Estimates of the standard molar free energy of formation of CupO(S) are also made. Praclicul consideration of this cell as an oxygen sensor for liquid metals is discussed briefly. SOLID mixed-oxide electrolytes which have a defect structure in the anion sublattice have recently become a very popular means by which the chemical potential of oxygen is measured at high temperatures. Since the pioneering work of Kiukkola and Wagner1 such electrolytes have been used in numerous cell studies for determining the thermodynamic properties of metallic oxides and oxy compounds, the partial pressure of oxygen in vacuum systems and other atmospheres, and the properties of oxygen dissolved in metals and alloys. The use of a solid electrolyte in a cell for a fast reliable method of oxygen determination in liquid metals would be a very important tool to the process metallurgist. In copper, for example, the oxygen content of the molten metal in the cathode furnace is a prime factor in determining the "set" or solidification profile of cast wire bars. In this investigation the activity of oxygen in liquid copper was measured by an electrochemical cell employing the electrolyte ZrO2 + 7 1/2 wt pct CaO. The cell used at 1100° and 1200°C was

Jan 1, 1967

By R. S. Dean

MANY studies have been made of the properties of steel produced by adding varying amounts of sponge iron to the charges used in steel-making furnaces.1-3 The results of these previous studies, however, have failed to disclose a reason for the belief of steelmakers that steel made in this way is definitely different from steel made entirely from scrap or iron melting stock. This paper deals chiefly with the structure of the sponge iron, of the wrought iron made by welding the sponge iron into blooms, and of the steel made by melting the forged and rolled blooms. It is believed that the structure of the final steel is inherited from the ore and that this inherited structure produces marked differences in the properties of the steel and explains the feeling of steelmakers which is based on their experience. Three kinds of sponge iron were used in this investigation: One made from a limonite ore reduced with natural gas, one made from a hematite ore reduced with natural gas, and one made from a magnetite ore reduced with charcoal. The sponge iron made by reduction with natural gas

Jan 1, 1935

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.' That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes' developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C' is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.', ' " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann's size modulus has been found convenient.' Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-' dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J'-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-'dx\

Jan 1, 1960

By Frederick N. Rhines

Because of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding their occurrellce, even though the fundamental mechanisms invalved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by Processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpiet the next. It is the purpose of the present Paper to present, by means of examples drawn from practice, a brief survey of the ways in which gas-metal diffusion serves and obstructs the Purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with ' but brief mention of parallel cases. The Nature of Gas-metal Diffusion The term ugas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of " substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain.temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. NO element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By George K. Burgess, Robert A. Hadfield

1. Introduction.—The methods of production of sound steel ingots have been described in several papers read recently before this Institute. It was thought by Director Stratton, of the U. S. Bureau of Standards, and ourselves to be of sufficient interest and importance, as a further contribution to this subject, to compare the properties of rails rolled in one mill according to American practice, from several types of ingot of substantially the same chemical composition but cast by several processes; and to compare in considerable detail the properties of an ingot manufactured by the Hadfield special-feeding process and one of the usual type for rolling into rails. We are greatly indebted to F. W. Wood, President of the Maryland Steel CO., who made this investigation possible by kindly placing his rail mill at our disposal; and he and his associates at Sparrows Point did everything possible to make the experiment a success, including the execution of several of the tests and analyses. 2. Classification and Manufacture of Ingots.—Of the ingots used in this investigation, eight were made in Sheffield and furnished by Sir Robert Hadfield, and one was made and furnished by an American steel company,l as a comparison ingot, and was supposed to represent the usual type of ingot from which rails are made. The characteristics of the ingots are given in Table I. Ingots 1, 2, 3, and 4 were cast large end up and fed by the Hadfield method in the usual manner with charcoal and blast continued until the molten steel has set on the top of the head, say varying from 20 to 40 min. To ingots 1, 2, and 4 was added 0.1 per cent. aluminum, and to the nickel-chrome ingot, No. 3, 0.125 per cent. For sake of comparison, there were also included two ingots, Nos. 8 and 9, cast with the small end up and fed by

Jan 1, 1915

By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By Tedsen L. F., Dorn J. E., A. E. Flanigan

since aluminum-alloy sheet may be used occasionally at moderately elevated ternperatures, the effects of temperature on the mechanical properties are of interest. Recently the short-time tensile properties of several high-strength materials have been studied at temperatures up to 3750°F.l This paper deals with stress-rupture and creep properties at the same temperatures. The work was done at the University of California as a portion of the project NRC-548. It was financed by the War Production Board and was supervised by the Office of Production Research and Development. This paper has been released for publication by the latter agency. The following materials were studied, all in the form of 0.040-in. sheet: Alclad 24s-T Alclad 24s-T8I Alclad 24s-T86 Alclad 75s-T R3oI-T (clad) Specimens were loaded in tension in the cross-grain direction. Testing temperatures included 94°F., 2II°F., 300°F., and 375°F. Stress levels were selected to cause rupture in times ranging from several minutes to 1000 hr. In each test the following data were obtained: (I) fracture time, (2) elongation at fracture, (3) the complete strain-versus-time curve (creep curve), (4) creep rate (defined in a later section). Materials Materials for specimens were obtained from the manufacturers' commercial

Jan 1, 1947

By R. D. Lee

A simplification of the method of Hurst and McCarty for conducting potentiometric model studies by the single probe method is presented along with experimentally determined invasion patterns for certain idealized flow problems. The analytical solution for one class of these problems is given. Finally, a general description is given of a newly developed instrument which permits direct mapping of flow lines and determination of transit times in potentiometric-model studies. Introduction The object of this paper is to present: I. A simplification of the method of Hurst and McCarty for conducting poten-tiometric-model studies of oil and gas reservoirs by the single probe method. 2. Results of a series of studies of certain idealized flow problems and the general conclusions to be drawn therefrom. 3. A description of a new instrument, the Chronocartograph, which greatly reduces the labor and time required for conducting potentiometric-model studies. Certain general conclusions may be drawn as results of the investigation of the idealized flow problems. They are: I. Injection and extraction areas should be separated by as great a distance as conditions permit since, in general, the recovery prior to first breakthrough tends to vary as the square of this distance. 2. Little advantage is to be gained by use of more than eight injection wells or groups of injection wells for the case of circular productive limits. 3. Elongated shapes of productive limits are best exploited by injection on the extended major axis only, with a line of extraction wells lying on the major axis. 4. The use of peripheral injection wells for elongated shapes is permissible, if necessary, but requires extension of the line of extraction wells. The exploitation of an oil or gas field is effected either by the expansion of the gas and oil, or by their displacement by another fluid. Both methods may be used simultaneously. When the displacement of the oil or gas is the controlling factor there arises the problem of mapping the progress of the boundary between the fluid in place and the displacing fluid. This problem is of particular interest in the operation of a cycling project in a gas-condensate field, where the wet gas is produced from one or more wells, commonly called "extraction wells.'' This wet gas is taken into a processing plant where the condensate is removed. The remaining "dry" gas is injected back into the field through one or more wells, called "injection wells," both to conserve the gas for future use and also to maintain the pressure in the field. In an operation of this type it is essential to anticipate the manner in which the dry gas will spread through the field, because the ultimate recovery of the wet gas depends

Jan 1, 1948