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By V. L. Elliott, C. L. Meyette

The conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a usable and relatively simple solution to a bothersome problem. Basis For Classifying In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will be used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined1 as a zone of

Jan 1, 1949

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By A. M. Gow

THE trend in ball milling has been toward mills of larger diameter, but without fundamental laws as a guide. The speeds at which mills are run have been a matter of cut-and-try. This paper deals with both diameter and speed and proposes to show the laws which apply to some laboratory ball mills, ranging in diameter from 18 to 42 in., run at various speeds. The correlation of power, speed, and grinding rate of the respective mills will be shown by curves of markedly significant similarity. Before presenting the results some consideration will be given to the mechanics of ball milling.

Jan 1, 1930

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

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

Jan 1, 1967

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By V. L. Elliott, C. L. Meyette

The conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a usable and relatively simple solution to a bothersome problem. Basis For Classifying In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will be used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined1 as a zone of

Jan 1, 1949

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

By L. W. Holm

This study shows that in the presence of foam, gas and liquid flow separately through porous media representative of reservoir rock. These results were obtained by using tracer techniques to measure the flow of the gas and liquid comprising the foam. Foam does not flow through the porous medium as a body even when the liquid and gas are combined outside the system and injected as foam. Instead, the liquid and gas forming the foam separate as the foam films break and then re-form in the porous system. Liquid moves through the porous medium via the film network of the bubbles and gas moves progressively through the system by breaking and re-forming bubbles throughout the length of the flow path. The flow rates of the gas and liquid are a function of the number and strength of the films in the porous medium. There is no free flow of gas; i.e., no continuous gas phase. On the basis of these results, foam can be expected to improve a water flood or gas drive by decreasing the permeability of the reseruoir rock to a displacing liquid or gas. This improves the mobility ratio and thus the conformance of the flood. INTRODUCTION Foam is formed when gas and a solution of a surface active agent are injected into a porous medium either simultaneously or intermittently. During the past few years, several papers have been published on the subject of foam flow in Dorous media. Foam has been used successfully in the removal of capillary water blocks from producing formations.''2 The use of foam in gas storage reservoirs to reduce gas leaks and to increase storage capacity has been considered in recent years. Foam has also been investigated as an oil displacing agent,3-5 and as an agent to improve the mobility ratio in a waterflood.6-10 However, the mechanism by which the gas and liquid phases comprising the foam flow through a porous medium has nor been described adequately. Normally, when two immiscible phases (gas and liquid) flow concurrently through a porous medium, each phase follows separate paths or channels. At given saturations of the two phases, a certain number of channels are available to each phase, and as saturations change, the number and configuration of the channels available for each phase also change. The effective permeability of each phase is a function of the saturation of that phase only, and the flow of each phase can be described by Darcy's law. When foam is present, the effective permeability of the porous medium to each phase is greatly reduced compaced with permeabilities measured in the absence of foam.6,11-13 Based upon the observed flow of surfactant solutions and gas in capillaries, it has been concluded that the gas and liquid may flow separately or they may flow combined as foam. At least four mechanisms have been postulated to explain how fluids flow with foam present: 1. A large portion of the gas is trapped in the porous medium and a small fraction flows as free gas, following Darcy's law.9 2. The foam structure moves as a body; the rate of gas flow is the same as the rate of liquid flow. 6,13 3. Gas flows as a discontinuous phase by breaking and re-forming films. Liquid flows as a free phase.12 4. A portion of the liquid and gas move as a foam body while excess surfactant solution moves as a free phase.14 It also has been suggested that different flow mechanisms exist for high quality (dry) foams made from dilute surfactant solutions and for foams made from more concentrated solutions. Studies conducted on the flow of foam through capillaries have shown that a plug-type flow occurs and that foam flows as a body.6,15 Fried also has described the flow of foam through porous media as

Jan 1, 1969

By J. Sharshall Grasty, Thomas L. Watson

The users of barite in the United States derive their supply partly from the domestic production and partly from the imports from foreign countries. According to the Mineral Resource division of the U. S. Geological Survey, the domestic production of barite in 1913 was 45,298 short tons, valued at $156,275, or $3.45 a ton, and the imports of crude barite were 35,840 short tons, valued at $61,409, or $1.71 a ton. These figures clearly show a decided advantage in cost of the foreign over the domestic barite to users in the United States. The difference in cost is the only advantage to the consumer of foreign barite, for there are large reserves of the mineral in the United States of good grade. The production of many of the operating mines is capable of decided increase, and it is believed that the operating mines together with the large reserves of undeveloped deposits of barite are entirely adequate to meet the demands of the users in the United States. Deposits of barite are known in California, Idaho, Nevada, and Alaska, but most of them are undeveloped because there is, apparently, no market for the material in that region. The domestic production is derived from Missouri .and the Appalachian States, the greater part being obtained from Missouri. Following the outbreak of war in Europe many users of foreign barite in the United States have been forced to seek their supplies at home. It seems opportune at this time, therefore, that a general review be given of the barite industry in the Appalachian States, one of the two areas from which the domestic supply of the mineral is derived, and that attention be directed to the undeveloped deposits in the region. Briefly, then, this paper reviews the barite industry in the Appalachian States, and describes the occurrence, preparation, and uses of the mineral. General Character Barite, known commercially as barytes or heavy spar, is barium sulphate (Baso4), containing when pure BaO, 65.7 per cent., and S03, 34.3 per cent. The specific gravity is 4.3 to 4.6, and the hardness 2.5

Jan 1, 1915

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By M. P. Tixier

In several log interpretation methods, water saturation is evaluated by use of the ratio of the readings of a short spacing resistivity device and a long spacing resistivity device plus information on the mud filtrate and connate water resistivities, which is often derivable from the SP. These methods are valid over a certain range of conditions, usually specified by moderate invasion and R.. greater than R,. Since these methods involve no explicit evaluation of the formation factor, F, the saturafiion so found may be used in the standard Archie equation to derive a computed formation factor which, as a check, may be compared with the formation factor known from other independent measurements. Discrepancies in the two values of formation factor generally indicate that the ratio method is not within its range of applicability. If the computed F is too low, the corresponding S, is too low; if the computed F is too great, the corresponding S, is too great. By means of this "porosity balance" check, and some knowledge of the probable conditions of invasion, the interpretation can often be improved. The poqosity balance check is discussed for the cases of the Induction-Electrical Log Interpretation Method, the Rocky Mountain Method, and the R.,/R, Method. For the first method, a discussion is also given for the case of shaly sands. INTRODUCTION Al though many logging tools are available to obtain a practical value of porosity, the only logging method reflecting the water saturation is electrical logging. Water saturation is commonly computed from electrical log data by means of the basic Archie formula, Where F is the formation factor, R, the resistivity of the formation water, and R, the true resistivity of the formation. One difficulty in this procedure is a possible error in the evaluation of R, from the logs— for example, in the case of very deep invasion. There is no possibility, inherent in the procedure, which would provide a check of the accuracy of R, and, hence, of the computed saturation. Other approaches have been proposed which are based essentially on the ratio of the readings made with two dzerent devices: one device, with a short radius of investigation, provides a value close to the resistivity of the invaded zone; the second device, with a long radius of investigation, gives a value close to the true resistivity of the bed. By these methods, the determination of saturation is made independently of any direct knowledge of the formation factor. Therefore, if the formation factor (or porosity) is known from other sources (core analysis, neutron log, MicroLog . . .), it becomes possible to take advantage of this additional information in order to check the value of saturation derived from these latter methods. Inasmuch as this proposed check procedure relies on a knowledge of the value of formation factor or porosity, it has been deemed appropriate to call this verification a porosity balance. The purpose of this paper is to discuss the principle and the application of the porosity balance, depending on the method of interpretation being used. Basis of the Method There are in existence three interpretation methods by means of which the water saturation can bc found without a knowledge of the formation factor (or porosity). As just stated, they are based on the fact that the ratio of the two resistivities (one measuring the resistivity close to the hole, the other measuring the resistivity far from the hole) is independent of the formation factor since it affects the two resistivity measurements in the same way. Chronologically, the resistivity ratio methods are: (1) the Rocky Mountain Method, which has been used since 1943 and was explained in a paper in 1949;' (2) the R../R, Method or Shaly Sand Method, presented in 1954, which permits the calculation of the water saturation in both clean and shaly sands2; and (3) the Induction-Electrical Log Method, presented in 1957 for the interpretation of the induction-electrical log combination." Each method requires certain definite conditions in order for the interpretation to be reliable. The porosity balance method will let us know whether these conditions are fulfilled. In clean formations we know that the fundamental Archie relation (Eq. 1) must always be verified. This relation can be rewritten:

By I. R. Kramer

Studies of the effect of size of the specimen on the change of slopes of Stages I and 11 by surface removal showed that the change of Stage I was independent of size with respect to the polishing rate; however, the change in the slope of Stage 11 with polishing rate increased directly in proportion to the surface area. The removal of the surface during the test affected the plastic deformation characteristics of gold, aluminum, and zinc single crystals and polycrystalline aluminum. The apparent activation energy of aluminum was found to be decreased markedly by removing the surface during the deformation process. In previous papers1-3 it was shown that the surface played an important role in the plastic deformation of metals. By removing the surface layers of a crystal of aluminum by electrolytic polishing during tensile deformation, it was found that the slopes of Stages I, II, and III were decreased and the extents of Stages I and II were increased when the rate of metal removal was increased. By removing a sufficient amount of the surface layer after a specimen had been deformed into the Stage I region, upon reloading, the flow stress was the same as the original critical resolved shear stress and the extent of Stage I was the same as if the specimen had not been deformed previously. The slope of Stage I was decreased 50 pct and that of Stage 11 decreased 25 pct when the rate of metal removal was 50 X 10"5 ipm. These data show that in Stage I the work hardening is controlled almost entirely by the surface conditions, while in Stages 11 and III both surface conditions and internal obstacles to dislocation motion are important. It appears that during the egress of dislocations from the crystal, a fraction of them becomes stuck or trapped in the surface regions and a layer of a high dislocation concentration is formed. This layer would not only impede the motion of dislocations, but would provide a barrier against which dislocations may pile up. In this case, there will be a stress, opposite to that of the applied stress, imposed on the dislocation source and dislocations moving in the region beyond this layer. It has been found convenient to refer to this layer as a "debris" layer. The "debris" layer may be similar to the dislocation tangle observed by thin-film electron microscope techniques.4 Reported in this paper are the results of studies on the effects of removing the surface during plastic deformation on aluminum crystals of various sizes. The effects of the surface on the yield point behavior of gold and high-purity aluminum crystals as well as the creep behavior were also determined. The effects of surface removal on polycrystalline aluminum (1100-0 and 7075-T6) are also reported. EXPERIMENTAL PROCEDURE For those portions of the investigation involving creep and tensile specimens, single crystals, having a 3-in. gage length and a nominal 1/8-in. sq cross section, were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The single crystals were prepared from materials which had initial purities of 99.997, 99.999, 99.999, and 99.999 pct for Al, Cu, Zn, and Au, respectively. The aluminum specimens for the size effect studies were prepared through the use of a three-tier mold in which crystals having a cross section of 1/8, 1/4, and 1/2 in. were grown from a common seed. The mold design was arranged so that one 1/2-in. crystal, two 1/4-in. crystals, and four 1/8-in, crystals of the same orientation could be cast. With this technique, it was possible to obtain only one set of crystals with the same orientation. Because of this limitation, it was not possible to determine both the changes of extent and slope of the various stages since a large number of crystals of the same orientation would have been required. Instead, only the change of slope as a function of the rate of metal removal was studied by abruptly altering the current density of the electrolytic polishing bath at various strains within the regions of Stages I and 11. The experimental techniques used for the tensile studies were essentially the same as those used previously.1,3 The specimens were deformed in a 200-lb Instron tensile machine, usually at a rate of 10-5 sec-5. A methyl alcohol-nitric acid solution was used as the polishing bath for aluminum. The temperature was maintained constant within ±0.l°C by means of a water bath. The tensile machine was

Jan 1, 1963

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,' in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

By T. C. Boberg, R. B. Lantz

This paper presents a method for calculating the producing rate of a well as a function of time following steam stimulation. The calculations have proved valuable in both selecting wells for stimulation and in determining optimum treatment sizes. The heat transfer model accounts for cooling of the oil sand by both vertical and radial conduction. Heat losses for any number of productive sands separated by unproductive rock are calculated for the injection. shut-in and production phases of the cycle. The oil rate increase caused by viscosity reduction due to heating is calculated by steady-state radial flow equations. The response of successive cycles of steam injection can also be calculated with this method. Excellent agreement is shown between calculated and actual field results. Also included are the results of several reservoir and process variable studies. The method is best suited for wells producing from a multiplicity of thin sands where the bulk of the stimulated production comes from the unheated reservoir. The flow equations used neglect gravity drainage and saturation changes within the heated region. INTRODUCTION This paper presents a calculation method which can be used to predict the field performance of the cyclic steam stimulation process. The calculation method enables the engineer to select reservoirs that have favorable characteristics for steam stimulation and permits him to determine how much steam must be injected to achieve favorable stimulation. While the calculation represents a considerable simplification of physical reality and the results are subject to numerous assumptions which must be made about the reservoir, it has been found that realistic calculations can be made of individual well performance following steam injection. The duration of the stimulation effect will depend primarily on the rate at which the heated oil sand cools which, in turn, is determined by the rate at which energy is removed from the formation with the produced fluids and conducted from the heated oil sand to unproductive rock. A complete mathematical solution to this problem is a formidable task, and finite difference techniques would undoubtedly have to be used. The calculation method pre- sented here utilizes analytic solutions of simple related heat transfer and fluid flow problems. The method is sufficiently simplified that it can be used as a hand calculation, although the calculations are somewhat lengthy and laborious. For that reason, the analysis was programmed for an IBM 7044 digital computer. Well responses observed at the Quiriquire field in eastern Venezuela&apos; have been matched using this program after making suitable approximations for reservoir and wellbore conditions. One of the most valuable uses of this calculation method is to assess the effect of reservoir and proc-cess variables on the stimulation response. This paper contains results of several studies made of key reservoir and process parameters. Among the most important of these is the influence of prior wellbore permeability damage. If a well is severely damaged prior to stimulation, a higher stimulation response will be observed than if it is undamaged. If a portion of this damage is removed, a permanent rate improvement will occur. THEORY I)ES(:KJJ&apos;TION OF CALCULATION METHOD The process of cyclic steam stimulation is essentially one of reducing oil viscosity around the wellbore by heating for a limited distance out into the formation through the injection of steam. Suitable modifications of the calculation technique presented here can be made so that stimulation of wells by hot gas injection or in situ combustion can also be calculated. A schematic drawing of the heat transfer and fluid flow considerations included in the calculation method is shown in Fig. 1. In brief, the calculation assumes that the oil sand is uniformly and radially invaded by injected steam. For wells producing from several sands, each sand is assumed to be invaded to the same distance radially. In calculating the radius heated rn energy losses from the wellbore and conduction to impermeable rock adjacent to the producing sands are taken into account. After steam injection is stopped, heat conduction continues and oil sands with r < ra cool as previously unheated shale and oil sand at r > r, begin to warm. The effect of warming of oil sand out beyond r, has little effect on the oil production rate compared to the effect of cooling of the oil sand nearer the wellbore than ra. Thus, in computing the oil production rate, an idealized step function temperature distribution in the reservoir is assumed where the original temperature exists for r > rn and where an average elevated temperature exists for r < rn. The average temperature in the oil sand for the region r < rn is computed as a function of

Jan 1, 1967

By Cyril Smith

SOMEWHAT over ten years ago the author described studies1,2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase bound-ary was accepted as substantially correct, even by later investigators3,4 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems" without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese¬silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced" to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polar-ized light and asserted that a new phase, not cubic, should be placed in the diagram adjacent to alpha. Sautner,13 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his dia-gram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4

Jan 1, 1939

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967