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By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

By W. J. Carlson, S. M. Parmerter, I. Iwasaki

This article discusses the effect of physical and chemical modifications of starches on the anionic and cationic flotation of silica from oxidized iron ores and magnetite-taconite concentrates. It also deals with the results of the interaction of starch, pH, and calcium ions on the flocculation, clarification, and filtration of iron ore slimes and magnetite-taconite tailings. Starches, particularly when an-ionically modified, were found to be effective depressants in anionic silica flotation. British gums and dextrins were beneficial for oxidized iron ores, but none of the starches or starch derivatives appeared to have any effect on magnetite-taconite concentrates. The flocculation and filtration of iron ore slimes were affected most strongly by the level of starch, to a lesser degree by the pH, and virtually not at all by the level of calcium chloride. The clarification of iron ore slimes was complexly dependent on these three factors. The flocculation of magnetite-taconite tailings depended mainly on the level of starch, whereas their clarification depended on the level of lime. As previously reported in the literature, selective flocculation and partial upgrading of a semitaconite could be readily attained with starch and calcium chloride. A previous article discussed some of the parameters that are important when various corn starches are applied to the soap flotation of activated silica from iron ores and to the flocculation of iron ore slimes.' Methods of solubilizing the starches and the molecular size after mechanical and thermal treatments, as inferred from the viscosity measurements, were shown to influence the adsorption characteristics on iron ores, and the residual concentrations of both calcium ion and starch in the pulp liquor were in direct correlation with the flotation and flocculation behavior.2-4 The present article summarizes the results of more recent tests conducted to ascertain the role of starches and starch derivatives in various phases of iron ore beneficiation. The scope of this investigation has been extended to include not only anionic and cationic flotation, but also the flocculation and filtration of iron oxide slimes, the selective flocculation and partial upgrading of semitaconites, and the flocculation and clarification of magnetite-taconite tailings —all problems that are of vital importance to the iron ore industry of Minnesota. By combining a practical approach with adsorption studies and by using single-mineral systems5 in these research efforts, it is believed that the ultimate goal of developing a suitable modification of starch structure may be realized. The topics covered in this article are limited to the empirical aspects of the research program on the depressant activity of starches and products in the cationic and anionic flotation of silica and of their role in flocculation, water clarification and filtration. ANIONIC SILICA FLOTATION In the soap flotation of activated silica from iron

Jan 1, 1970

By Armantrout C. E., R. S. Dean. J. R. Long T. R. Graham, Roberson A. H.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By K. Tangri, M. Chaturvedi

On water-quenching from within the (a + ß) phase region Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys can undergo w transfirmation. This transformation has been attributed to the enrichment of ß Zr phase, at the solution-treatment temperature, by the solute atoms. The ß—w transformation is accompanied by a hardening 01 the alloys and in the optimum condition w-bearing specimens of the ternary alloy are about 14 pct harder than those bearing only a' phase. On aging crl reverls thermally to more stable phases, which results in a considerable softening of the specirnens, as follows: w quenched -waged + ß Zr (enriched) waged - a + ß Nb The high-temperature bcc ß Zr in certain zirconium alloys can transform to a metastable w phase which has a primitive hexagonal structure. In the Zr-Nb alloy system w phase has been observed in the composition range of 7 to 15 wt pct Nb by a number of investigators.'-' In this composition range w can form by water-quenching ß Zr or by aging. known as athermal and thermal w, respectively. Hatt and Roberts' have found that thermal w has a constant c/a ratio of 0.622 +0.002 regardless of the composition and tha: the lattice parameters are of the order of a = 5.02A and c = 3.0 ?. The actual lattice parameters depend upon composition and the temperature of aging. The lattice constants of athermal w. however, depend upon alloy composition.3 The presence of w phase in zirconium alloys can cause substantial strengthening which has been attributed as probably due to the coherency between w and parent ß Zr phase. Robinson et al.' found that the presence of w can raise the strength of Zr-5.0 Nb-2.0 Sn and Zr-5.0 Mo-2.0 Sn alloys to about 170.000 psi: however. the ductility is considerably reduced. With the growing use of Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys in the nuclear reactors, and the significant effect of w transformation on the mechanical properties of zirconium alloys studies were undertaken to study the w transformation in Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys. This paper is concerned with the formation and reversion of w phase in these alloys. 1) MATERIALS AND EXPERIMENTAL TECHNIQUES The following two alloys were studied: 1) Zr-2.5 Nb-0.5 Cu (referred to as the ternary alloy): 2) Zr-2.5 Nb (referred to as the binary alloy). The chemical analysis of the alloys is given in Table I. The alloys, in the form of 3/8-in.-diam rods and 1/8-in.-thick sheets, were supplied by the Chalk River Nuclear Laboratories of the A.E.C.L. Initial fabrication for preparation of various specimens was carried out by cold rolling and swaging with intermediate anneals at 1000°C. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-% m of Hg. For optical metallography and hardness measurements disc specimens + in. diam by + in. thick were used. After the required heat treatments the specimens were mechanically and then chemically polished in a 45 pct HNO3, 45 pct H20. and 10 pct HF solution. The hardness measurements on the chemically polished specimens were carried out on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative hardness value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using copper K-a radiations in 114.6-mm-diam camera. Thin films for transmission electron microscopy were prepared by electropolishing heat-treated a by 7 by 0.005-in.-thick strips using a modified Bollmann-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol electropolishing bath was kepl at -5OCC and polishing was done at 5 to 10 v. The thinned specimens were washed in ethyl alcohol at -30" to -40°C and dried between filter papers. The thin films

Jan 1, 1970

By C. S. Barrett

IT has been observed that deformation in iron takes place by slip on {110} + {112} + {123} planes1,2 but in silicon ferrite with low deforma-tion temperatures or high silicon contents (exceeding 4 per cent) the authors have found that slip is confined wholly to {110} planes, at least with small amounts of deformation. The purpose of the present inves-tigation was to determine the effect of this alteration of slip mechanism on preferred orientations in cold-rolled and recrystallized strips. Inci-dental observations on the effect of the recrystallization temperature were also made. The numerous determinations of the texture of cold-rolled iron and steel have been in satisfactory agreement as to the principal features of the texture. (with the exception of a few conclusions that apparently have been based on insufficient data). The texture is chiefly one in which [110] directions of the grains lie along tile direction of rolling, with a deviation of a few degrees, and in which the (100) planes lie in the plane of the rolled sheet, with a deviation from this position chiefly about the rolling direc-tion as all axis 3-9. This deviation about the rolling direction as an axis has been measured by different observers and lies between about 45° and 50° or 60° for iron5,6,9 and is usually in the neighborhood of 50° for mild steel6,7,8. The range of this deviation is a function of the percentage of total reduction 8, 10. Post' reported that it decreases with increasing percentage reduction, but apparently he .studied only the surface material, which Gensamer and Mehl7 found to be somewhat differently oriented from the material in the inside of the sheet. McLachlan and Davey10 found that the deviation also decreases with increasing percentage of total reduction for the material in the interior of the sheet and is independent of the percentage of reduction per pass.

Jan 1, 1937

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

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

Jan 1, 1921

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By C. W. Nicolson

The Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large and elaborate mining and milling plants. Most of the leases were

Jan 1, 1940

By U. F. Kocks

The flow stress in some latent slip systems of aluminum and silver crystals after various deformations in single slip was investigated by transverse compression and supplemented by experiments on overshoot of the compression axis and the stability of corner orientations. Work hardening was found to be remarkably isotropic, the ratio of the flow stress in the latent system to that in the primary system being between 1.0 and 1.3. The strain-rate dependence was not significantly larger in the latent system. This low anisotropy suggests that specific dislocation interactions are not the direct cause of work hardening. Either the obstacles are essentially impenetrable so that only their distance enters, or a fairly random distribution of dislocations of all systems is. in fact. formed during single slip. The latter seems to he excluded by the observations on the strain-mte dependence and on the amount of secondary strain. The amount of seconzdary strains occurring in single slip was determined by shape-change mensurements and by a new method connected with the latent-hardening experiments. It is definitely less than 1/300 times the strain in the primary svstem. WORK hardening is due to dislocation interactions; this is a hypothesis, and possibly the only one, on which all present work-harden ing theories agree. About a dozen specific interactions have been considered, and it is unlikely that any essential one has been missed. Different work-hardening theories differ to a large extent in the specific interactions which are deemed most important. The presence or absence of any particular interaction, and its degree, depend on the geometrical relationships between the two dislocations interacting. Let us enumerate some examples. Two dislocations may react, with a varying reaction energy, to form a third dislocation, and this reaction product may be sessile or glissile. Two dislocations may intersect and a jog may be formed on both, on one of them, or on neither; this jog may be sessile17Z or glissile and it may, if moved nonconservatively, lead to the production of vacancies or interstitials. Finally, a dislocation may bypass another one and thus interact only with its stress field. All these interactions depend on the specific relation between the Burgers vectors and line directions of the two dislocations. Any dislocation generated during plastic deformation of fcc crystals belongs to one of twelve slip systems. Taking any one dislocation, its relationship to each of the other eleven can fall, by symmetry, into one of only five classes. These relationships are enumerated in Fig. 1 and Table I. Each slip system is represented in the stereo-graphic projection by two triangles, namely those in one of which the specimen axis would have to lie if the specimen were to deform in single slip on this slip system in a given sense, in a tension test. Let us represent the primary slip system by the shaded triangles. The other slip systems are classified only with respect to their relationship to this primary system. The code letters (initials of established names* in German) are explained in Table I. Three specific interactions are also listed in cases where they may be strong: the product of a reaction, the formation of jogs in either system, and the elastic bypass stress. The last column relates to the types of experiments reported in this paper and summarizes their results. To decide experimentally between the relative importance of the various interactions one would like to produce a group of dislocations in one slip system and then measure the stress necessary to force another group of dislocations of a specific second system through them. Hopefully, one can produce the first set of dislocations by plastically deforming the specimen in single slip. Then one can try to achieve single slip in a specific, previously latent system and measure its flow stress. If it is different from the virgin flow stress, there has been "latent hardening". Some types of latent-hardening experiments will be discussed in the next section. The strain-rate and temperature dependence of the flow stress is an indication of the importance of dislocation intersections. By extending an investigation of this dependence to the latent systems, one can determine how much more important forest contributions are here. seeger3 has used the as-

Jan 1, 1964

By R. W. Raymond

This name is applied to the present mining law, as enacted in 1872 and since, to indicate its leading characteristic—in which it differs from all previous mining laws of this or any other country. The earlier act, passed in 1866, was practically the first attempt of Congress to deal with the question of mining titles upon the public domain. It was framed after nearly twenty years of acquiescence on the part of the Government in the self-constituted tribunals, officials, rules, and customs of the mining districts. In its recognition of these, and in several other particulars, the act of 1866 was open to serious criticisms. It is the purpose of this paper, not to trace the history of legislation on this subject, or show in detail what were the faults of the earlier law, but rather, by a discussion of certain aspects of the present law, to point out how great a revoluition it has effected in the rights of mining locators, and to indicate some of the difficulties attending its application. In the attempt to correct the vagueness of the act of 1866 an entirely new elernent was introduced into the law, bringing with it a new set of difficulties. Under the act of 1866 and the miners' customs which it followed, the lode was the thing claimed and subsequently acquired by patent. And the claim to a given number of feet on the longitudinal course of the lode was rooted in 'a discovery of any part of the lode in any part of the claim. ("Extensions" could in many districts—perhaps universally—be located and claimed on the strength of the discovery in the principal claim to which they referred; but this is a point not essential to the present discussion.) It was not necessary to find the outcrop or the upper edge of a lode in order to lay a valid location upon it. An explorer, sinking a shaft and intersecting a lode not already discovered and claimed by another, could claim by that discovery the number of feet along that lode which the local laws might permit (not exceeding the maximum set by the United States statute) whether his sur-

Jan 1, 1884

By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick's first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank' supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains' Glasstone, et al' treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity' has shown how to convert the Onsager equations to a form very similar to Lamm's. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-

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

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By J. E. Lamar, J. S. Machin

INSULATING materials include a wide variety of nonmetallic mineral products such as exfoliated vermiculite, expanded gypsum, 85 pct magnesia, diatomite, asbestos, perlite, cellular glass, pumice, silica aerogel, expanded aggregates and mineral wool. Except mineral wool, most of these products, or the materials from which they are manufactured, are described in other chapters of this book. PROPERTIES OF INSULATING MATERIALS The insulating properties of the materials considered in this chapter result in general from entrapping extremely small pockets of air in such a manner that heat is not transferred by convection. The minimum heat conductivities of such insulating materials are slightly greater therefore than the conductivity of still air. In addition, conductivity varies with the overall density of the material, the temperature range in which the measurements are made, and the form into which the material is fabricated. However, the numerical value of heat conductivity should not be the sole criterion of an insulating material; for a particular application it may be advantageous to use a material of somewhat higher conductivity in order to secure other desirable engineering properties. This is especially true with certain materials that are used because of their refractoriness. Comparative insulating values of some commonly used insulating materials are shown in Table 1. In comparing the values presented in this table it should be borne in mind that heat conductivity varies with the mean temperature, with the overall density, and with the amount of moisture present. With fibrous or granular materials it varies with fiber or grain size and with the amount and kind of binder, if any is used. Under some circumstances it may vary with the arrangement of

Jan 1, 1949

By R. E. Ogilvie, A. R. Kaufmann, S. H. Gelles

The solid-solubility limits of iron in beryllium were determined between 850o and 1200oC by analysis of differential type multiphase diffusion couples, using an X-ray absorption technique. The maximum value of the solubility limit was found to be 0.92 ± 0.02 at. pct (5.46 wt pet) at the eutectic temperature 1225°C. The solubilities of nickel and beryllium were determined between 900°and 1200°C by the same technique and the maximum solubility was found to be 4.93 + 0.01 at. pct (25.2 wt pet) at the eutectoid temperature, 1065°C. A previously unreported high-temperature phase which decomposes eutectoidally at 1065 °C was found to exist in the beryllium-nickel system at a composition of approximately 8 at. pct Ni (36 wt pet) by diffision-couple analysis. The presence of this phase was confirmed by thermal analysis and metallo-graphic analysis of the structure resulting from the eutectoid decomposition. G. V. Raynor1 has treated the solid solubilities of some of the elements in beryllium on the basis of the "Hume-Rothery" rules2 which have been modified to include ionic size and ionic distortion effects. It was predicted that the solubility of iron and nickel in beryllium should be slightly less than that of copper. The lowering of the solubility, according to Raynor, is due to a more unfavorable relative valency effect and an ionic size effect. Kaufmann and corzine3 have compiled data on the solubilities of elements in beryllium and have discussed them in the light of the Raynor paper. These authors feel that, because the elements having the greatest solubility in beryllium systematically fall in the Group VIII and IB Columns of the periodic table, the electronic structure greatly influences the maximum solid solubility of elements in beryllium. The solubility of iron in beryllium was determined by Teitel and cohen4 as part of the study of the beryllium-iron phase diagram. The determination was carried out by X-ray and thermal analysis and according to the phase diagram presented, the maximum solubility of iron in beryllium is 0.41 at. pct (2.5 wt pct) at 1225oC. However, it is estimated that the uncertainty in the position of the a-beryllium primary solid-solution boundary is about 0.5 at. pct (3wtpct). Losana and Goria3 in studying the beryllium-nickel phase diagram, determined the solid solubility of nickel in beryllium by thermal analysis. They found the maximum solubility to be between 1.65 and 2.65 at. pct (10 to 15 wt pct) at 1240°C. This value decreased rapidly with decreasing temperature. In determining approximate ranges of solubilities for different elements in beryllium, Kaufmann, et al,8 reported a value of between 1.3 and 1.7 at. pct (7.9 to 10.1 wt pct) for the solubility of nickel in beryllium. The value was obtained by metallographic examination of quenched alloys and lattice-parameter measurements. However, the authors also noted a single-phase structure for a 1.7 at. pct Ni alloy (10 wt pct) on cooling from the liquid. This would indicate a higher solubility range than was reported. ~isch,' in his X-ray studies of beryllium-copper, beryllium-nickel, and beryllium-iron intermetallic compounds, reports the disappearance of a second phase (Ni,Be2) in the beryllium primary solid solution at approximately 4 at. pct (20 wt pct). THEORY The analysis of concentration gradients in diffusion couples has proven to be a useful tool in determining phase equilibria.8-14 In this particular study the diffusion couples were chosen to straddle the expected composition range of the phase boundary, then heat treated at a given temperature and the concentration gradient evaluated. The composition of the phase boundary for a given temperature appears at a point of discontinuity of the composition gradient. Examples of typical phase diagrams and the concentration gradients which should be found in such systems are shown in Fig. 1. In the present work, gradients of the form of Fig. l(c) were obtained in diffusion couples made of pure beryllium and two-phase alloys of beryllium with either iron or nickel. The composition at the point where the gradient becomes discontinuous, Cs, corresponds to the solubility limit of either iron or nickel in beryllium. The analysis of the concentration gradients was carried out by an X-ra absorption method developed and applied by Ogilvie and later used by Moll13 and Hilliard.l4 It depends on the fact that the absorption of X-rays by matter is determined by the concentration and type of the various atomic species present. The relationship for the intensity, I, of a monochro-

Jan 1, 1960

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well's actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2'' O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2'3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5'6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

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 R. P. Rothwell

Jan 1, 1885

By R. T. Keyes, R. B. Clay, L. L. Udy, V. O. Cook, M. A. Cook

Based on compressibility and stress wave velocity in rock, initial explosive loading conditions, the thermochemistry of the explosive and reasonable description of the pressure-distance relations behind the shock front, the distribution of energy between the products of detonation and the burden are estimated as a function of time for various loading conditions. These include 'powder factor', loading density A (fraction of borehole occupied by explosive), and the explosive itself. Factors responsible for rock fragmentation are discussed in terms of: 1) 'release wave fracturing', 2) 'shear wave fracturing', and 3) 'release of loading fracturing' or 'rock bursting'. Release wave fracturing appears to occur only in the immediate vicinity of free faces, and shear wave fracturing only adjacent to the borehole under normal blasting conditions. Rock bursting is thus considered to be the most important means of rock fracturing in blasting. Means for maximizing it are considered. The most important factors to consider include maximum available energy A, explosive density p1, loading density A and 'powder factor'. Maximum efficiency is attained in general by maximizing the A . p1 product. This is achieved by using high density explosives at a loading density of unity (A = 1.0). Ways for achieving this condition are discussed. The bulk-handled aluminized slurry blasting agents have the desired properties for achieving optimum conditions for high blasting efficiency based on the theory outlined herein. Factors considered most important in the blasting of rock are: 1) The maximum available energy A, determined by the heat of explosion Q and the mechanical efficiency ?, a factor intimately associated with the mode of application (A = Q at highest gas concentrations). 2) The 'borehole pressure', pb, or the maximum pressure developed in the borehole after passage of the detonation wave and before the burden has had time to move or become compressed appreciably. (Owing to the short duration of the detonation wave at any particular point in the borehole, the fact that the explosive may not always fill the borehole completely and the further fact that the burden may not actually see the detonation pressure, the borehole pressure is considered more significant than the detonation pressure p2 as a performance factor in borehole blasting.) The borehole pressure is determined by the explosion or adiabatic pressure, p3 , and the loading density, A, or the fraction of the borehole filled by explosive. 3) The physical conditions important in the application of the explosive are: a) The 'powder factor,' (We/Wr), or the ratio of the wt of the explosive to that of the rock being blasted expressed as lb per ton or more generally in lb/cu yd. b) The bulk density, p1 ?. c) The 'burden' or 'line of least resistance,' the spacing between boreholes, the geometry of the borehole pattern and sequence of firing. d) The physical and chemical properties of the rock, most significant of which are possible heterogeneties, such as faulting, prefracture, and greater than micro-scale chemical heterogeneities. (This factor is not considered here but deserves a great deal of careful consideration.) All of these factors need to be carefully considered in the most economical engineering of a blast. Here is considered firstly an outline of the present status of dynamic rock mechanics, particularly as it pertains to blasting. The factors pertaining to the most efficient application of blasting agents are also considered, followed by a discussion of methods of application to achieve optimum explosives performance. ROCK MECHANICS Dynamic rock mechanics is currently a rapidly developing science contributing greatly to a better understanding and consequently the more effective application of explosives in blasting of rock.1-22 Basic to the development of the science of dynamic rock mechanics were the advances of Goransen23 and the Los Alamos and NOL groups24-28 concerning rock and stress wave phenomena and the transmission and reflection characteristics of stress waves at interfaces between different media. Basing considerations on this new knowledge as well as new experimental methods of study (ultra-high speed streak and framing cameras and electronic timers) the theory of fracture and failure of solids under impulsive loading by stress waves developed rapidly.14,16,27-29 Also the

Jan 1, 1967

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2'3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5'6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938