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By B. M. Larsen, T. E. Brower

Introduction and Summary By "thermochemical factors" we refer to those variables which affect the net heat which must be put into the bath in order to make a heat of steel from any given set of charge materials. This is admittedly only one phase of the production rate problem. The whole problem includes also consideration of rate of charging, flame radiation intensity, rate of optimum fuel input obtainable without undue damage to the furnace structure and any variations in conditions such as stirring, slag volume or viscosity which affect the rate at which heat can flow down and away from those exposed surfaces where the heat is first received from the flame. Because a given type of charge in a shop is often considered as being nearly constant in both physical and chemical characteristics from one heat to another, and because such a state of affairs may be thought of as resulting in a reasonably constant net heat requirement, this requirement is usually neglected as an invariable, inevitable matter, about which nothing can be done. With normally variable charge, and variable percentages of limestone and cold pig, however, the net heat requirement can be subject to very appreciable change; it may also be affected by such things as the currently popular procedure of blowing oxygen into the bath. To bring the general problem of production rate into better perspective, therefore, it seems worthwhile to try to evaluate the net bath heat requirement and the amount by which it may change through variation in different factors. Because our calculated values of net heat are admittedly uncertain, we have tried to check them in part by statistical data on actual production rates over rather large groups of commercial heats. The results of calculation of net heat requirements in a wide range of actual commercial practices may first be summarized briefly. We find a wide range between the extremes of different practices, as would be expected, with duplex practice (essentially blown metal plus hot metal) having essentially a zero net heat requirement, an all-cold charge practice somewhat over I million Btu per ton of steel and a high hot metal practice about 0.75 million Btu per ton. Over the commercial range of scrap plus hot metal practice, increasing the percentage of hot metal from 40 to 78 pct, with other factors nearly constant, decreased the net heat by only some 5-10 pct. The net heat is increased by about 1.2 pct for each I pct of the metallic charge present as cold pig. Calculated values of oxygen supplied by air varied from about 25 up to 60 lb per ton of steel, and in a 60 pct hot metal practice, an increase from 32 to 52 Ib oxygen from air decreased the calculated net heat from 0.88 to 0.74 million Btu per ton. Use of pure cold oxygen to substitute for about one half of the total charge ore (about 28 Ib oxygen replacing 145 Ib ore per ton of steel) decreased the

Jan 1, 1949

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By C. R. Kuzell

ALTHOUGH furnaces constructed of refractory brick have been oper-ated for many decades, there has always been an unfulfilled desire by the operators for a less arduous and more satisfactory method of patching weak spots and burned-out zones in order to postpone and to effectively extend the termination of a furnace campaign. Not only has this desire frequently arisen when small spots have approached incipient failure while the furnace structure as a whole was still in good condition, but also when larger areas showed signs of needing replacement. The availa-ble methods have been arduous, sometimes dangerous, inefficient with respect to the life of new refractory material used, and nearly always have necessitated interruption of the continuity of the furnace operations and therefore reduction in furnace production during the period of time required for the repair work. Most of these older methods have involved the replacement of masonry by refractory shapes in the weakened areas. Many attempts have been made to develop a method of patching the burned-out areas by spraying granular refractory material upon old surfaces. While some success has been attained in attempts to renew the grooved, corroded side walls and fettling, and the edges of hearths, there have been no known successful applications of the spraying method in patching the underside of arches of operating furnaces. The method developed recently at the Clarkdale smelter of the United Verde Branch of Phelps Dodge Corporation, at Clarkdale, Ariz., and described in this paper, has been found to be not only convenient and successful with respect to patching vertical or inclined surfaces, but has met with a marked degree of success in patching the parts of furnace arches that are exposed to flame, the successful result being obtained with-out interruption or interference with the continuity of furnace operations. ? It may be described as a method of renewing the interior refractory sur-faces of operating furnaces by pneumatic spraying of an aqueous suspen-sion of finely divided particles of refractory material. It has been used

Jan 1, 1939

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 I. R. Kramer, P. D. Gorsuch, D. L. Newhouse

Although many methods have been suggested for the calculation of tensile strength and yield point from chemical composition, their usefulness has been limited to a particular cooling rate or section size. Further limitations have been imposed by failure to take into account many of the alloying elements that exert a considerable influence on the tensile strength or yield point. These systems, nevertheless, have filled an important need in many instances. The value of a system for the calculation of the tensile properties from the chemical composition and cooling rate is that it permits the prediction of the effect of alloying elements and heat-treatment on the mechanical properties, so that more efficient use of alloying elements may be made. Furthermore, it aids in the choice of steel for a given application aid tends to decrease the number of steels that otherwise would have to be tested. It is the purpose of this work to present a method of calculating tensile strength and yield point from the chemical composition and to suggest a method of correlating the tensile-strength and yield-point factors and cooling rate. Steelmakers have been interested for many years in the calculation of the tensile strength of hot-rolled steels. Quest and Washburn' summarize several of the attempts that have been made to devise formulas. They show the inadequacy of each of these formulas and present one of their own. It is apparent from their work that a simple additive equation of the type TS = A + BX + Cy + DZ + . . . , where A, B, C, D, etc. are experimentally determined constants and x, y, z, etc., are the percentages of alloying elements present in the steel, is not adequate to analyze fully the situation encountered in the calculation of tensile strength. For example, it was found that the difference between the calculated and observed values became progressively greater as the carbon and manganese contents were increased. Therefore, the effect of manganese was given as a function of the carbon content. Grossmann, in his work on the harden-ability of quenched steels, and Walter, in his method of calculation of tensile strength of normalized steels, present two cases in which multiplying factors were successfully used to express the combined effect of alloying elements. The factors in both cases were obtained from the fractional increase in hardenability or tensile strength with increase of alloy content. Yield point often is more important in design than tensile strength. For quenched and tempered steels a linear correlation exists between yield 2nd tensile strength.4 This is not true, however, for normalized

Jan 1, 1948

By William Grady

FACTORS entering into the market value of coal are its grade, and the cost of labor, material, and capital. Reduction in these costs cannot be expected in the future, and it therefore follows that greater economy in their use must be accomplished if it is desired to hold the present markets; more tons of product per unit must be obtained in a given time from both men and material, and means devised for increasing the percentage of lump and domestic sizes. This paper is presented for the purpose of inviting discussion and stimulating thought in regard to the influence of methods of procedure and plans of mining, upon the quality of coal, the economical use of labor, material, and capital, and the cost of production. Even the better methods of the. present day leave much to be desired, and a review of the reasons and necessities for their use may be of value in pointing the way to more economical mining. The writer does not attempt to discuss untried methods of mining, but rather to state clearly and concisely a summary of the results obtained under the several methods of procedure that have been adopted. In some instances a high degree of concentration has been effected, and comparisons of the results obtained with the results of lesser degrees of concentration form an interesting study. It is believed that much may be accomplished in improving the quality, and in the more economical use of labor, material, and capital, by concentration, and it is to concentration in particular that your study is invited. The writer, who .has occasion to visit many mines, most of which ire under different management, has been inclined to the opinion that improvement has been retarded in many ways and that mining has not as yet been entirely freed from the early-day practices which were forced upon it.

Jan 5, 1915

By J. M. Schopt

COAL petrology is the study of the lithologic composition and texture of coal and includes megascopic as well as microscopic differentiation. Coal petrography is a quantitative study, principally (but not exclusively) microscopical in nature. The distinction between coal petrologic and coal petro-graphic studies usually is not important, but it is important to recognize that these studies differ materially from other types of petrology that deal primarily with minerals. The petrologic entities* of coal are less clearly distinguished than most minerals and the basis of distinction is not always clearly expressed. The relation of coal petrology to geologic, mining, and technologic problems is most evident when results of coal petrologic studies can be stated quantitatively. The chemical and physical composition of coal and the determination of its quality and properties are continuing problems. The source of these problems lies in the heterogeneity of coal and in its almost complete insolubility in ordinary solvents at normal temperatures. The empirical and comparative character of standard chemical coal analytic values is one of the consequences resulting from heterogeneity and insolubility of coal. Nevertheless, these coal analytic methods are highly technical and diversified. Coal petrol.ogy employs a group of similar analytical methods which provide information about coal that the other methods cannot supply. The heterogeneity of coal is most clearly demonstrated by means of petrologic studies. The properties utilized in coal petrologic studies are related to texture (size, form, and association), hardness, light reflectance, and light absorption and transmission (color). Size relations are most evident but are commonly overlooked. Coal is classed chemically as a mixture, and chemical analyses thus show the composition of the sample as a whole. Geologically coal is an organic clastic deposit, derived from diverse plant fragments and particles having a size range comparable to that of a conglomerate or breccia. The mixture of different materials that compose coal, large and small, can be realized only by microscopic study. This is because the fundamental cellular units of plants, from which coal is formed, are microscopic in size. The kinds of altered plant particles and fragments in coal have specific differences in hardness, reflectance, and color that signify differences in composition. These differences must be taken into account in evaluating the aggregate properties of coal. Terminology and Texture Full discussion of terms applied by various petro-logists in analysis of coal is beyond the scope of this article. For convenience the simpler types of petrologic entities that are defined without reference to lithologic occurrence or texture will be called coal components. Fig. 1 lists reactive and relatively inert

Jan 1, 1957

By P. D. Gorsuch, I. R. Kramer, D. L. Newhouse

Although many methods have been suggested for the calculation of tensile strength and yield point from chemical composition, their usefulness has been limited to a particular cooling rate or section size. Further limitations have been imposed by failure to take into account many of the alloying elements that exert a considerable influence on the tensile strength or yield point. These systems, nevertheless, have filled an important need in many instances. The value of a system for the calculation of the tensile properties from the chemical composition and cooling rate is that it permits the prediction of the effect of alloying elements and heat-treatment on the mechanical properties, so that more efficient use of alloying elements may be made. Furthermore, it aids in the choice of steel for a given application aid tends to decrease the number of steels that otherwise would have to be tested. It is the purpose of this work to present a method of calculating tensile strength and yield point from the chemical composition and to suggest a method of correlating the tensile-strength and yield-point factors and cooling rate. Steelmakers have been interested for many years in the calculation of the tensile strength of hot-rolled steels. Quest and Washburn' summarize several of the attempts that have been made to devise formulas. They show the inadequacy of each of these formulas and present one of their own. It is apparent from their work that a simple additive equation of the type TS = A + BX + Cy + DZ + . . . , where A, B, C, D, etc. are experimentally determined constants and x, y, z, etc., are the percentages of alloying elements present in the steel, is not adequate to analyze fully the situation encountered in the calculation of tensile strength. For example, it was found that the difference between the calculated and observed values became progressively greater as the carbon and manganese contents were increased. Therefore, the effect of manganese was given as a function of the carbon content. Grossmann, in his work on the harden-ability of quenched steels, and Walter, in his method of calculation of tensile strength of normalized steels, present two cases in which multiplying factors were successfully used to express the combined effect of alloying elements. The factors in both cases were obtained from the fractional increase in hardenability or tensile strength with increase of alloy content. Yield point often is more important in design than tensile strength. For quenched and tempered steels a linear correlation exists between yield 2nd tensile strength.4 This is not true, however, for normalized

Jan 1, 1948

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By H. E. Wilborg, G. V. Henderson

This chapter deals with those sands employed by foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal is poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened by either heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%), and occurring in numerous locations thoughout the United States. Consumption End Uses Foundry sands fall into four distinct categories: silica sand, lake sand, bank sand, and natural molding sand. Silica sand is a general term used to describe washed, graded, dried, and cooled clay-free sands which are found in many parts of the United States. They generally contain 90 to 100% silica but vary greatly in chemical analysis and grain structure. Lake sand is the sand dredged from Lake Michigan or dug from the dunes bordering that lake. Bank sand is composed primarily of silica grain but containing up to 5% clay. It is shipped in both the damp and dry state but the normal processing of bank sand consists only of drying and scalping. Occasionally two different grades of bank sand are blended prior to or during loading. Natural molding sand is a term used to describe a sand containing sufficient clay as mined to be suitable for molding purposes. Clay content may vary from 10 to 24% with the balance of the material consisting primarily of silica sand. These sands range in fineness from one peaked on the 20 mesh to one which contains more than 50% of the particles passing the 270 mesh. Lake sands are relatively coarse and are used in great quantities for the production of automotive castings. Bank sands and natural molding sands are gradually phasing out as the production of castings becomes more a science and less an art. The vast majority of foundry sands used today are those known as the silica sands and lake sands. Foundry sands are used in two basic ways. The majority are used in the green or uncured state with the balance used in the cured or set state. Green sand is grain bonded with clay and contains varying amounts of water to plasticize the clay in order to bond the grains together. Green sand is either naturally bonded or "synthetic" sand. The naturally bonded molding sands are generally found in the Hudson River Valley of New York State, Cumberland County in New Jersey, and in Tennessee and Mississippi. Synthetic sand is molding sand compounded in the individual foundry. It is made up primarily of graded silica sand, western or southern bentonite, water, and carbonaceous and/or cellulosic materials. Green sand is used primarily in making molds. The use of naturally bonded green sand has been declining for many years, primarily because naturally bonded sands are more difficult for the foundryman to find and control. Synthetic green sand, on the other hand, can be

Jan 1, 1983

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By Charles E. Nelson

THIS paper will outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as jar as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper and will be discussed briefly.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, this paper will deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. The outline of this discussion will closely follow that of an earlier paper,2 with such changes and additions as seem necessary to bring it up to date. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux, which provides protection during melting and a molten pool of flux into which the solid magnesium melts. The flux is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies;, on quiet standing, it separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is desirable. The open-pot method is used generally in the following processes: (I) alloying and remelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drys out or thickens after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to

Jan 1, 1946

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By Herbert H. Uhlig

ALTHOUGH the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldlo summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.15 per cent carbon. He noted: From these comparisons it will be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable. Ib His data showed that alloys containing 4 to 10 per cent manganese water-quenched from 1000°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 870°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loringa reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 540°C. (1000°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.15 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <0.001 per cent P). In this paper it is shown that of the low- carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from 1000°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By W. A. Krivsky, R. Schumann

Relaxation calculations were made to find the temperature distribution in the refractory wall surrounding a tuyere pipe. One set of boundary conditions approxiwated those of a standard copper converter while a second set represented a hypothetical,thermally insulated tuyere pipe. The pvonounced cooling effect of the tuyere is related to the problem of tuyere accretions and tuyere bunching. PARTICULARLY severe service conditions are encountered in the tuyere zone of a basic copper converter during the matte blow. High-temperature gradients result from the juxtaposition of the hot charge and the tuyere pipe carrying cold air. Refractory temperatures near the tuyere mouth vary rapidly with time when the blast is turned on or off. One of the most serious problems is the formation of magnetite accretions around the tuyere mouth, which occurs very rapidly under some operating conditions. As a result, continual punching of the tuyeres is necessary to maintain a satisfactory rate of converting. Thus, if some means could be devised for keeping the tuyere pipes fully open without necessity for punching, a considerable saving should result from reduction in labor cost, maintenance of full capacity operation, and reduction in refractory costs. Recent quantitative studies of the FeO-Fe,O,-SiO, system1 have shown that the solubility of magnetite in iron-silicate slags decreases rapidly with de- creasing temperature in the range of copper converting temperatures. Data taken from the previous work are shown in Fig. 1. Thus the formation of "horns" and accretions around the tuyere mouth can result simply from the freezing out of magnetite on the cooler areas of refractory immediately adjacent to the tuyere pipes. One might expect to find a correlation between the severity of magnetite formation and the area of refractory surface which is cooled below the freezing point of the slag (corresponding to magnetite precipitation). Magnetite itself has a very high melting point (1597°C) so that the accretions are for all practical purposes infusible. The accretions might be dissolved by increasing the silica content of the slag and at the same time raising the temperature, but this approach is not feasible because it results in rapid corrosion of the basic refractory lining of the converter as a whole. In order to understand better the problems involved in tuyere design and operation, it seems essential to have at least a semiquantitative idea of the thermal conditions in the tuyere zone. Accordingly, this paper presents results of thermal calculations for an idealized copper converter tuyere. These calculations follow the so-called relaxation

Jan 1, 1960

By B. M. Larsen, T. E. Brower

Introduction and Summary By "thermochemical factors" we refer to those variables which affect the net heat which must be put into the bath in order to make a heat of steel from any given set of charge materials. This is admittedly only one phase of the production rate problem. The whole problem includes also consideration of rate of charging, flame radiation intensity, rate of optimum fuel input obtainable without undue damage to the furnace structure and any variations in conditions such as stirring, slag volume or viscosity which affect the rate at which heat can flow down and away from those exposed surfaces where the heat is first received from the flame. Because a given type of charge in a shop is often considered as being nearly constant in both physical and chemical characteristics from one heat to another, and because such a state of affairs may be thought of as resulting in a reasonably constant net heat requirement, this requirement is usually neglected as an invariable, inevitable matter, about which nothing can be done. With normally variable charge, and variable percentages of limestone and cold pig, however, the net heat requirement can be subject to very appreciable change; it may also be affected by such things as the currently popular procedure of blowing oxygen into the bath. To bring the general problem of production rate into better perspective, therefore, it seems worthwhile to try to evaluate the net bath heat requirement and the amount by which it may change through variation in different factors. Because our calculated values of net heat are admittedly uncertain, we have tried to check them in part by statistical data on actual production rates over rather large groups of commercial heats. The results of calculation of net heat requirements in a wide range of actual commercial practices may first be summarized briefly. We find a wide range between the extremes of different practices, as would be expected, with duplex practice (essentially blown metal plus hot metal) having essentially a zero net heat requirement, an all-cold charge practice somewhat over I million Btu per ton of steel and a high hot metal practice about 0.75 million Btu per ton. Over the commercial range of scrap plus hot metal practice, increasing the percentage of hot metal from 40 to 78 pct, with other factors nearly constant, decreased the net heat by only some 5-10 pct. The net heat is increased by about 1.2 pct for each I pct of the metallic charge present as cold pig. Calculated values of oxygen supplied by air varied from about 25 up to 60 lb per ton of steel, and in a 60 pct hot metal practice, an increase from 32 to 52 Ib oxygen from air decreased the calculated net heat from 0.88 to 0.74 million Btu per ton. Use of pure cold oxygen to substitute for about one half of the total charge ore (about 28 Ib oxygen replacing 145 Ib ore per ton of steel) decreased the

Jan 1, 1949

By C. O. Fairchild

THE meaning of temperature control can be extended to cover not only the control of temperatures&apos; but also the control of processes through a knowledge of the temperatures involved. In this sense it has a very wide interest. A list of the industries in which temperature control is used in one way or another would cover nearly the entire industrial field. This discussion will be confined to the field of high temperatures. In practically all industries involving operations at high temperatures, pyrometers are used or men are paid for their ability either to estimate temperatures or gage an operation by some physical or chemical change or condition dependent on temperatures. As progress is made in the development of instruments and of methods for measuring temperature, some of these highly skilled artisans are learning the use of a new tool. Many processes have been, in recent years, improved by means of exact measurement thus substituted for estimation, but in a great many industries the pyrometer has had practically no opportunity to demonstrate its usefulness. The perfecting of instruments must be accompanied with a dissemination of the knowledge that new instruments are available and can be economically used. The demand at present, however, is ahead of the supply, and many industries are handicapped by the want of pyrometers. One of the highest paid skilled tradesmen of the present time is the man in the steel rolling mill who knows when proper working temperatures are attained. The metallurgist in his development of steels is continually demanding closer adherence to given temperature ranges in the processes, and the pyrometer is rapidly becoming indispensable. Properties of the finished products are being correlated with working temperatures and so closely that in some cases even the pyrometer is taxed to give the required accuracy. The greatest progress has been made in those industries in which the lower temperatures are used, particularly below 500° C. In this lower range automatic control has been highly developed.

Jan 9, 1919

By C. R. Johnson, R. A. Greenkorn, R. E. Haring

Three confined five-spot miscible displacements at unity, favorable, and unfavorable mobility ratios were conducted in a shallow, water-saturated sandstone of Pennsylvan-ian age near Chandler, Okla. These studies, plus associated laboratory experiments, were designed to measure miscible displacement performance in a controlled natural system, using known scaling criteria to develop an approach to modeling the heterogeneous field system. We have concluded from these studies that: (I) displacement efficiency in the field is a pronounced function of mobility ratio, indicating that miscible fingering observed in simple laboratory models occurs in the field: (2) field displacements can be quantitatively predicted by scaled laboratory models if the degree and location of field permeability variations are preserved in the models: and (3) arbitrary simplifications of heterogeneity will not necessarily predict observed displacement efficiency, and the simpler the model, the more optimistic the prediction. INTRODUCTION Many processes to achieve miscible displacement of reservoir oil by injected fluids have been conceived and field tested by the oil industry. Among the better known are high-pressure gas, enriched gas, and LPG banks. The simplest form of miscible displacement—one fluid miscibly displacing another fluid of different viscosity but the same density—has been studied extensively in homogeneous laboratory models. Observations of unstable fingering have been made which explain the significant decrease in displacement efficiency as the mobility ratio (ratio of displacing fluid mobility to displaced fluid mobility) increases. General industry experience with field tests of miscible displacement projects, mostly LPG banks, has been premature solvent breakthrough and lower than predicted production rate increases. These results have been attributed to either unstable fingering, unusual or unexpected permeability stratification, or both. Miscible displacement data in a controlled natural system have never been reported, however. Also, it has not been shown that properly designed and constructed laboratory models quantitatively predict field-scale behavior. The purpose of the combined field and laboratory ex- periments reported in this paper is twofold. The first was to measure miscible displacement performance at different mobility ratios in natural rock approaching field size under precise, controlled conditions. The second purpose was to utilize known scaling criteria plus several approaches to heterogeneity to model the field. Comparison of model and actual field results should then determine whether or not the laboratory phenomena (manifested by miscible displacement efficiency) are exhibited in large, natural rock systems. We carried out our program by first locating a shallow, water-saturated reservoir whose rock properties were representative of oil-bearing reservoirs. Detailed reservoir description by core analysis and interference testing showed the field site to be heterogeneous. A sequence of controlled, aqueous-phase miscible displacements was conducted at unity, favorable and unfavorable mobility ratios. A central, confined pattern was used to obtain the displacement data. A laboratory program using sand-packed models was conducted to determine the modeling criteria necessary to simulate field behavior of miscible displacement in a heterogeneous system. SCALING THEORY The detailed derivations and descriptions of the scaling laws that apply to laboratory models of reservoirs are adequately described elsewhere, so the following discussion will be restricted to facets of importance in this study. For a displacement in which one liquid miscibly displaces another, the following dimensionless groups are required to have the same numerical value in the model as in the field: The model also must be geometrically similar to the field, be spatially oriented the same as the field (same dip angle), and have the same initial and boundary conditions as the field (same initial fluid saturations and same injection-production well arrangement). When these conditions are satisfied, the theory predicts that at dny dimensionless time (pore volumes of produced fluids) the dimen-sionless flow potential and dimensionless fluid concentrations will be identical at all dimensionless spatial locations within the model and the field. If this prediction is correct, then the local dimensionless velocities must be identical, thus the instantaneous fraction of displaced fluid produced and the cumulative recovery expressed as fraction of original fluids in place must be identical at all dimensionless times. The theory outlined above has been obtained by either dimensional analysis or inspectional analysis of differential

Jan 1, 1966

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir&apos;e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5&apos;11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard&apos;s method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970