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By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By R. U. Fitting, A. C. Bulnes

Field experience with limestone and sandstone production indicates the existence of wide differences between the reservoir behavior of these two types of formation. Little attention appears to have been given to the separate study of the flow of fluids and the retention of fluids in limestones. This paper presents data and arguments to demonstrate the existence of a difference between the two types of formation, and urges the separate intensive investigation of limestone reservoirs. AH experimental data presented pertain to dolomitic limestone formations in west Texas and New Mexico. Two kinds of Porous media are recognized— intergranular and intermediate. Intergranular rocks are those in which the porosity and permeability are determined by the geometrical properties and the sorting of the sedimentary units; intermediate rocks, those in which there is no direct relationship between grain properties and the porosity and permeability. Limestones in general are intermediate media. The partial relationship between porosity and permeability of any class of Porous media is represelried by an area of .finite extent and definite shape on the permeability-porosity plane. The horizontal and vertical variations of porosity and of permeability in limestone and sandstone formations are discussed and compared. Comparisons are made of connate-water content, the relative permeability-saturation relationship, and capillary phenomena in the two kinds of rocks. A number of tentative conclusions are drawn relative to the reservoir properties of lime- stones; in particular, (I) dolomitic limestones are oil bearing and apparently are oil productive in zones of permeability less than 0.1 millidarcyj and (2) primary depletion (by gas expansion) oil saturations may be lower in dolomitic limestones than in sandstones. Introduction It is well known that the reservoir performance of limestones displays numerous irregularities when compared with that of sandstones, and that the departures from "normal" behavior of limestones are more frequent and generally more marked than in sandstones. This is particularly true of fractured limestones and those that have undergone considerable development of secondary porosity' A review of the literature of production research published during the past 15 years reveals a startling absence of theoretical and experimental investigations directed specifically toward explaining and predicting the performance of limestone reservoirs, even. though such problems as the prediction of water encroachment and the estimation of ultimate recoveries continue at the "inspired guess" stage. By far the greater part of the experimental data reported pertain to measurements on sandstone core samples, while the theoretical studies, almost without exception, are developed from the assumption of an ideal porous medium and therefore seldom are applicable to limestone formations. The chief cause of this situation appears to be the common belief that, to all practical intents and purposes, sandstones and the majority of producing limestone formations

Jan 1, 1945

By H. H. Rachford

Numerical solutions of immiscible flow problems in which dispersive effects of capillarity are dominated by convection require excessively fine grid spacing with attendant high computing costs. The use of coarser spacing reduces cost but often produces oscillation or undue dispersion associated with displacement fronts, A numerical formulation is proposed here which should be applicable to two-dimensional flow problems. it is in part analogous to an approach previously tested for miscible systems. The convective transport is approximated using a change of variables to yield a coordinate system moving approximately with the local characteristic velocity. The capillarity-induced dispersive terms in the differential system describing the process are approximated with respect to a fixed coordinate system by the usual implicit formulation. One-dimensional tests of the procedure yielded results in which the saturation profiles tended smoothly to the zero-capillary pressure solution as the ratio of viscous to capillary forces was successively increased in a sequence of calculations. This contrasted favorably with solutions by other numerical procedures which would require attendant grid refinements to approach the zero capillary pressure results. INTRODUCTION Numerical solution of displacement problems has until recently relied on applying methods developed primarily for transient heat-flow problems. Such problems are classified as parabolic in type, and where the heat transport is purely by diffusion their solutions are characterized by a high degree of smoothness. It is not surprising, therefore, that for approximating these solutions available finite difference methods are quite adequate. In flow problems the transport is partly by diffusion, partly by convection or flow. Although the problem remains of parabolic type because the dispersive effects of capillary forces or diffusion play some role in every displacement, at high flow rates the problem is dominated by convection, and solutions tend toward those of equations of the hyperbolic type. Solutions of hyperbolic problems are characterized by the translation of fronts, or discontinuities, that may progressively increase in sharpness. Numerical methods for treating parabolic problems become less and less satisfactory as displacement rates increase and the role of dispersion due to concentration or capillary pressure gradients becomes small relative to transport due to flow. In computation the difficulty manifests itself as an error associated with the grid size chosen. 1-6 In summary, if the heat-flow type approximations are to include the terms arising due to convection, one of several choices may be made: (1) an upstream (to the direction of flow) approximation for the convection terms may be used; (2) a centered-in-distance (CID) approximation may be used; or (3) a recently developed approximation based on the theory of oscillation matrices may be chosen.6 The last appears to have significant promise for one-dimensional flow problems; its extendibility to two or three dimensions is an open question. In either of the first two approaches, a suitably small ratio of v&/D must be maintained, where v is the velocity, & is the grid spacing and D the effective dispersivity in the direction of flow. In the first choice, the approximation of the convective part is only first-order correct and errors introduced appear as a numerically induced dispersivity of magnitude proportional to v?x. In the CID choice, the approximation can be second-order correct, but the difference formulation fails to satisfy the maximum principle unless a condition on v?x/D is met. Practically, this means that for high flow rates oscillatory solutions may result in the neighborhood of a front unless exceedingly small grid intervals are taken. While the procedure proposed by Stone and Brian4 permits a less severe limitation to be placed on this ratio, ultimately the flow rates increase relative to the dispersivity the oscillation obtains. Further, extensions of their approach to higher dimensional systems may be attended by considerable

Jan 1, 1967

By C. W. Volek, J. E. Chappelear

The injection of a hot liquid into initially cool porous media, saturated with the same liquid and surrounded by two impermeable but heat conducting media (cap and base rock), has been studied both experimentally and theoretically. The temperature dependence of the viscosity was included in the theoretical model, but it was assumed that the specilic heats and densities of the various materials were independent of the temperature. Solutions to the theoretical model were approximated by numerical methods. Both theoretical and experimental results indicate that center-line temperatures are significantly higher than boundary temperatures. Comparison of experimental and theoretical results with a cold/hot viscosity ratio 01 19:1 were in reasonable agreement. Theoretical calculations show that the effect of the temperature dependence of viscosity was very significant at ratios of 100:l to 1000:1, which are typical of those that occur when injecting hot water to flood heavy oil reservoirs. INTRODUCTION We consider the problem of prediction of fluid flow and temperature distribution in an initially cold-fluid-filled reservoir on the injection of the same hot liquid by the use of mathematical and physical models. The results reported are for a two-dimensional rectangular section of the reservoir, as shown in Fig. 1. The injection and withdrawal faces are assumed to be equipotentials for fluid flow. The ultimate purpose of such models would be to predict hot-water injection performance. However, we note that in the work presented here, one of the most significant aspects of the problem — the instabilities resulting from two-phase, water and oil flow — is not included. We will not give a historical review, but refer instead to the paper of Spillette and Nielsen,1 which contains a rather complete bibliography and critical discussion. The physical problem is exactly the same as Spillette and Nielsen, except for certain simplifications in our assumptions. The mathematical details are somewhat different, and we will present the details of our method here. The mass flow equation, which is elliptic in character, is handled by successive overrelaxation. The heat flow equation, which is parabolic in character, is handled by a straightforward explicit approximation. Some difficulty arose in the over-all heat balance due to small errors in the solution of the mass flow equation, and we feel that a different formulation of the heat flow equation would be desirable for future work. In addition to the mathematical solutions for the temperature distributions in a porous medium due to the injection of hot liquids, experimental data are presented to check the validity of these solutions. A schematic diagram of the model is shown in Fig. 2. Certain qualitative physical conclusions were obtained from our numerical and experimental results. These are: 1. Assuming high (infinite) conductivity normal to the bedding plane in the reservoir is a poor approximation, and may lead to overestimates of the total heat losses (to cap and base rock) of as much as 50 percent. 2. More heat is retained in the reservoir (per unit of heat injected) for higher viscosity changes. 3. Any particular temperature isotherm moves more rapidly along the center line for higher viscosity changes. Consequently, the approximation of temperature independent viscosity is not suitable for obtaining quantitatively correct results. MATHEMATICAL MODEL Our mathematical model is that of a reservoir of thickness 2h. The problem is idealized from that of a linear hot-water drive, and we imagine that the input face is sufficiently far away from the injection wells that the stream lines enter it normally. Similarly the production wells are far enough from the outflow face that the flow lines leave it normally. The reservoir and surrounding cap and base rock

Jan 1, 1970

By S. S. PRENZ

Discussion held at the sessions of the Canal Zone meeting, November, 1910. [SECRETARY'S NOTE.-As a result of this discussion, an expression of opinion covering all points of unanimous agreement was adopted and signed by members of the Institute party as individuals. This statement, which was printed in the Bulletin of December, 1910, is reprinted below, as an introduction to ,the detailed report of the discussion. It should be clearly understood that it does not constitute an official declaration by the Institute, the rules of which forbid any such action. At the New Haven meeting of February, 1909, a free discussion of the plan of the canal took place, in which the critics of the present scheme had full opportunity to state their views. That discussion was continued at considerable length in the newspapers ; but the Institute was never committed to either side. In this latter instance, the situation is precisely similar. Certain members and guests of the Institute, having had the advantage of later developments and of personal inspection, have expressed the conclusions at which they have arrived on their own responsibility ; and these conclusions are published by the Institute, subject to further discussion, like any other part of its proceedings. The general statement referred to contained a promise that the full discussion, of which it was a result, would be subsequently printed ; and this promise is fulfilled, so far as practicable, in the subjoined report, concerning which I beg to offer the following explanations: 1. It is made up of the remarks of the members of our party, as subsequently written out and mailed to the Secretary. 2. In editing these contributions, I have condensed the material considerably by cutting out much repetition of opinions and phrases ; and in such excision, I, frankly confess, the authors whose communications were delayed, have been the sufferers. Nevertheless, there is a good deal of repetition left, as there must be, when so many persons had talked so much, and come to agreement upon so many points. 3. It has been found impossible to preserve in this report the actual order of the free and informal oral discussion represented. Consequently the several contributions have been arranged in alphabetical order under the names of their authors. References to "preceding speakers," etc., must therefore be construed as referring to other speakers, preceding or following.-R. W. R.] S. S. PRINZ AUGUST WILHELM, AT SEA, November 14, 1910. We, the undersigned, members and guests of the American Institute of Mining Engineers, after a visit to the Isthmus of Panama, and inspection of the work of the United States Isthmian Canal Commission, and after full discussion of our individual impressions, find ourselves in unanimous agreement as to the following conclusions:

Jan 1, 1911

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation." The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation.76 The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By C. T. Liu, J. Gurland

The deformation behavior in tension of spheroidized carbon steels was studied at room temperature as a function of carbon content, 0.065 to 1.46 wt Pct, and carbide particle size, 0.88 to 2.77 p. It was found that the Hall-Petch strength-grain size relation is directly applicable to the yield and flow stresses of the two lower-carbon steels , 0.065 and 0.30 pct C. The strength data for the medium- and high-carbon steels, 0.55 to 1.46 pct C, also satisfied the Hall-Petch relation, provided that these data are based upon the particle spacing. Beyond 4 pct strain, the flow stress data of all the steels studied could be represented by the same Hall-Petch relation with dinerent spacings for grain boundary and particle strengthening. The behavior of the higher-carbon steels was consistent with the postulated formation of a dislocation cell network during processing and initial deformation (up to 4 pct strain). The cell size was assumed to be equal to the planar particle spacing. The true stress at the ultimate tensile strength was also found to be a function of the particle spacing. At a given temperature and strain rate, the yield and flow stresses of carbon steels depend on the type and dimensions of the microstructure. Starting with the work of Gensamer et al. in 1942,' experimental studies on pearlitic and spheroidized carbon steels revealed that the strength of steels is a function of two main parameters: the ferrite grain size2'3 and the carbide particle spacing;1'4'5 on this basis, two different strengthening mechanisms have been developed to apply to steels of low and high carbon contents, respectively. In polycrystalline iron and mild steels the grain boundaries are regarded as the major structural barriers to slip. The relation between strength and grain size is generally represented by the Hall-Petch equation which is based on a linear proportionality between strength and the inverse square root of the average grain size.2'3y677 However, Gensamer et al.' and Roberts et related the yield strength of medium -and high-carbon steels to the carbide particle spacing alone, and they found a linear relation between the logarithm of the mean free path in the ferrite and the yield strength in both spheroidized and pearlitic steels. By means of the electron microscope, Turkalo and LOW' extended the study to finer structures; they concluded that the logarithmic relation is not valid for the entire range of microstructures unless grain boundaries are also included in the measurement of the mean free path. For the specific case of spheroidized steels, Ansell and aenel' found that the yield strength data,4'5 when plotted as a function of mean free path, fit the Hall-Petch equation; however, T'ysong found that the same data fit the 0rowanl0 relation if a planar inter-particle spacing is used. Recently Kossowsky and ~rown" studied the strength of prestrained spheroidized steels, 0.48 and 0.95 pct C, and concluded that the strength due to the carbide dispersions varies linearly with the reciprocal of the square root of the mean free path between carbide particles and dislocation networks. Such networks were first observed by Turkalo." The conclusion common to all these studies is that the available slip distance in the ferrite is the most important variable in determining strendh. Previous work on carbon steels is restricted to limited composition and strain ranges. The mechanism which governs the flow properties is not clearly understood, and, in particular, little is known about the composition dependence of the transition between grain boundary strengthening and particle hardening. The purpose of the present work is to investigate the strengthening mechanism in spheroidized steels over a wide range of carbon content, 0.065 to 1.46 wt pct, and plastic strain, yielding to necking. The spheroidized structure was chosen because of its relative simplicity and the relative ease of control and measurement of the structural parameters. The experimental work is limited to tensile testing at room temperature at constant extension rate. The effects of the carbide particles on the fracture behavior of spheroidized steels are discussed elsewhere.13 EXPERIMENTAL PROCEDURE Eight different grades of vacuum-cast carbon steels were supplied in the form of forged and rolled plate by the Applied Research Laboratory of the U.S. Steel Corp. The compositions furnished with these steels are given in Table I; the carbon content ranges from 0.065 to 1.46 wt pct, or from 1.0 to 22.3 vol pct of carbide. The steel plates were cut transversely into rods a little larger than the test specimens, 1 in. gage length, i in. diam. The rods were austenitized in air (enriched with CO by a consumable carbon-rich muffle) at 50° C above theA, orA., temperature for 2 hr and then quenched in oil with vigorous stirring. The as-quenched rods were tempered in two stages in order to obtain the desired distributions and sizes of carbide particles. The rods were first tempered at 460° C for 10 hr and then at 700" C for periods ranging from 4 hr to 3 days, in vacuum. After final machining, all specimens were vacuum-annealed again at 650°C for 1 hr in order to relieve residual stresses. The tension tests were carried out in two steps. The initial part of the load-strain curve, up to about 2 pct strain, was determined on a Riehle testing machine with an extensometer of small strain range, 4 pct strain, in order to obtain the yield and initial flow piopertiesi As soon as the first part of the test was finished, the specimen was placed in an Instron testing machine equipped with a strain gage extensometer with a maximum strain range of 50 pct. The load-strain curve to fracture was

Jan 1, 1969

By J. W. Cuthbertson, R. A. Cresswell

THE constitution of Cu-rich alloys with 1.5 to 13.5 pct Sn and 0.25 to 3.0 pct Be and the precipitation-hardening characteristics of alloys with 1.5 to 13.5 pct Sn and 0.25 to 1.0 pct Be have been examined. The hardness and tensile strength of the alloys examined increase markedly after solution treatment at 700°C followed by heat treatment at temperatures between 200" and 450°C. By a combination of cold work and heat treatment, hardness values similar to those exhibited by commercial Be-Cu alloys containing 2.25 pct Be can be obtained with ternary alloys containing 9 pct Sn and 0.75 pct Be and containing 10 pct Sn and 0.5 pct Be. Marked hardening effects occur with alloys containing even less beryllium. By heat treatment alone, a hardness value of 310 diamond pyramid hardness can be obtained from an alloy containing 10 pct Sn and 0.75 pct Be. Preliminary tensile tests have shown that an ultimate tensile strength of 110,000 psi with an elongation of 23 pct is obtainable by precipitation hardening an alloy with 8 pct Sn and 0.75 pct Be. The precipitation-hardening process has been followed microscopically for certain alloys and the inference is that, while the initial hardening effect is probably explained by the precipitation of the ß phase of the Cu-Be system, further hardening, proceeding at a much slower rate, also occurs, apparently as a result of precipitation of phases of the Cu-Sn system, particularly precipitation of the 6 phase at temperatures below 350". The presence of the e phase of the Cu-Sn system in certain alloys at temperatures below 350°C has been confirmed. Tin-bronzes are widely used in engineering applications where a combination of high strength and good resistance to corrosion is wanted. The maximum strength is induced in these alloys by cold working, and it would be an advantage for many purposes if high strength could be achieved alternatively by an age-hardening process. While Cu-Sn alloys have a good fatigue resistance they can be surpassed in this respect by Cu-Be, but the use of the latter alloy is limited by its high cost. If, by adding beryllium to tin-bronze, the properties of the respective binary alloys could to some extent be combined, a most attractive alloy should result. As pointed out by Raynor,¹ beryllium is on the borderline of the zone of favorable size factors for copper, and the solid solubility of beryllium in copper is consequently much more restricted than if the size factor were strongly favorable. The size factor is sufficiently favorable, however, to permit an increase in solid solubility with rise in temperature, and there is thus a composition range in which CU- Be alloys are susceptible to hardening by precipitation heat treatment. Although the a phase of the Cu-Sn system is similarly susceptible to precipitation treatment, the time necessary to establish equilibrium in commercial alloys of this type is usually so great that age hardening becomes impracticable. The addition of beryllium to Cu-Sn alloys would appear to offer a means of conferring on the latter useful age-hardening properties. Masing and Dahl² and others have, in fact, shown that the addition of beryllium to Cu-Sn a solid solutions renders these alloys susceptible to precipitation hardening and after such hardening confers on them an encouraging improvement in physical properties. If this improvement could be achieved by the addition of substantially smaller amounts of beryllium than are customarily found in binary Cu-Be alloys, the ternary alloys should possess economic advantages which might make them more attractive than the binary alloy for some applications. Binary Systems Copper-Tin: The constitution of these alloys is now reasonably well known and is summarized in the equilibrium diagram published by Raynor.³ The following observations, due to Raynor,¹ on the structure of those phases of the Cu-Sn system that are likely to be found in the ternary alloy system will facilitate the subsequent discussion on the examination of that system. The ß phase is an electron compound at the electron-atom ratio 3:2 and has a body-centered cubic crystal structure. This phase is stable only down to 586°C, at which temperature it decomposes eutectoidally into the a and y phases. The y phase has a structure that is also based on the cubic system. This phase is stable down to 520°C, at which temperature it decomposes eutectoidally into the a and d phases. The d phase is an electron compound (Cu³¹Sn8) which has a crystal structure analogous to that of 7 brass. This phase is stable from 590" to 350°C; on prolonged annealing at the latter temperature it breaks down into a mixture of the a and E phases. The e phase is an electron compound (Cu³Sn) having the electron-atom ratio 7:4. Its structure may be regarded as a superlattice based on the close-packed hexagonal system. This phase is stable from 676°C to room temperature. The primary solid solubility of tin in copper increases to a maximum of 15.8 pct as the temperature falls from that of the peritectic reaction to 586°C. The solid solubility remains constant from 586" to 520°C. At lower temperatures the solubility decreases progressively. Below 350°C the fall in solubility is pronounced and is associated with the precipitation of the e phase. This precipitation is very sluggish and does not normally occur under service conditions. Copper-Beryllium: The Cu-Be system has been investigated by Borchers' and others. Raynor5 summarized the present state of information on it.

Jan 1, 1952

By S. S. Marsden, S. A. Khan

Externally generated foam was injected continuously into short porous media. Both flow rate and pressure drop were measured. Liquid saturation was determined by electrical conductivity. Foam yuality I, expressed as the ratio of gas volume to total volume, was varied from 0.70 to 0.96. As measured with a modified fann VG Meter, apparent viscosity of this foam µa decreases with increasing shear rate but usually falls within the range of 50 to 500 cp. At a given shear rate, µa increases almost linearly with I-. When measured with a Bendix Ultraviscoson, kinematic pa is independent of V but absolute pa increases with T from about 3 to 8 cp. The effective permeability -apparent viscosity ratio ke/µa decreases almost linearly with V for porous media of high permeability, but the rate of decrease becomes less for tighter ones. The relative permeability-apparent viscosity ratio kr/µa us V data does not fall on a single line. The kr/µa ratio increases with liquid saturation in the porous medium and with surfactant concentration. Estimates of pa for foam in porous media vary from 30 to 100 cp. INTRODUCTION Although research on the development of a foam-drive, oil recovery process has been going on for almost a decade, most of the significant publications have appeared within the last several years. This illustrates well the rate at which interest in this process is accelerating. Bond and Holbrook 1 were the first to describe the use of foam to improve oil recovery in their patent of 1958. They proposed that an aqueous foaming agent slug be injected into the formation and that this be followed by gas to produce a foam in situ. Fried 2 studied the injection of foam into porous media which had already been subjected to conventional gas or water drives and found that gas could be used to drive a foam bank which would, in turn, displace additional oil in the form of an oil bank. He attributed the increased oil recovery to the high effective viscosity of foam flowing in porous media. His microscopic observations showed the importance of foam generation and regeneration within the porous medium. By injecting both air and aqueous surfactant solution, Bernard3 generated foams within the porous medium in which oil displacement was being studied. In a separate empirical test, he also measured the dynamic foaming characteristics of the same surfactants in water and/or oil. With some exceptions and for the seyen surfactants studied, there seems to be a qualitative relationship between the efficiency of liquid rlisplacrment and the dynamic foaming testtsed. This relationship was not consistent enough to eliminate the necessity of actual foam flood tests in porous media for surfactant selection. In a study basic to gas storage in aquifers, Bennett4 described the displacement of brine by foam in consolidated porous media. Among other things, he stated that the ability of a surfactant solution to foam is more important than the stability of its foam. The presence of a foam bank between the displacing air and the displaced brine improved both breakthrough and ultimate recovery. In a continuation of this work Kolb5 attributed the great reduction in surfactant solution production rate as displacement by air progressed to a decrease in relative permeability to gas. These several effects reported by both Bennett and Kolb can all be attributed to the high apparent viscosity of foam which was obviously flowing in the porous media. Bernard and Holm6 observed that gas permeability in the presence of foam was much less than in the absence of foam when both were measured at the same gas saturations. This reduction in permeability was proportionately greater for more permeable sands and sandstones than for the less permeable. Viscosities of the surfactant solution and air were used for their calculations rather than apparent foam viscosities. The foam stability increased with decreasing permeability, which was probably due to the natural regenerative properties of porous media, and the permeability reduction increased

Jan 1, 1967

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-

By Bunting S. Crocker

PEBBLE grinding at Lake Shore is not a temporary wartime substitute. The tube milling plant, with a 1000 ton per day capacity, grinds a hard siliceous ore to 90 pct - 325 mesh. The plant, prior to using pebbles, was consuming 4.3 lb of 1 1/4-in. grinding balls per ton of ore, which amounted to 785 tons of balls per year. At September 1951 prices, $132.60 per ton, this steel cost amounted to, $104,400 per year, or $0.285 per ton milled. By the Lake Shore method of substituting screened rock for this steel, all of this cost is saved. This is one of the major economies in Lake Shore mill practice. Regardless of the ultimate price of grinding balls, a change, back to steel balls is not considered. The present pebble plant is more flexible than a steel ball plant and equally efficient. For example, if it is desired to change the size of grinding media, the pebble charge in any mill can be changed completely in 4 to 5 days, as against 76 days to change completely a 1 1/4-in. steel ball charge. To change pebble size it is necessary only to change two sets-of screens and clean out the rock feed storage bin. This will take 8 to 10 days as against 3 to 4 months to clean. out the customary supply of grinding balls kept on hand. Also it has not always been ' possible to purchase all desired sizes of balls at any price. In an analysis of savings effected by the use of the pebble mills, the flexibility of the Lake Shore grinding plant should be discussed, as it has a direct bearing on these savings. The plant has always used several units to handle tonnage rather than sending all the tonnage through a single unit. This principle may result in using small diameter mills, but no objection to that is seen. At no time has any advantage been found in cost per ton ground in large diameter mills. Both the capacity and the power of any mill varies as the diameter raised to the 2.6th power. Consequently large or small mills are equally efficient, and a plant should be designed to use as many units-or combination of units as is consistent with reasonable operating practice. Mills under 5 ft diam are harder to reline, etc. To define the case at Lake Shore, .2600 tons per day formerly were milled in seven 7x6-ft ball mills and twelve 5x16-ft (and two 6x16-ft) tube mills.* This gave an excellent test plant. and an extremely efficient-one. In this plant the ratio of ball mills to tube mills was 1: 2. When the much cheaper pebble mills were substituted for the tube mills, this. ratio -was changed to one ball mill to four pebble mills to take the greatest possible advantage of the cheaper operating mill, i.e., the pebble mill. This flexibility without loss in efficiency has been an important item in the cost savings. It is interesting to note that the use of pebbles for fine grinding was. proved first in the laboratory in a 12-in. ball mill. In fact, since 1934 all testing on -.8 mesh material has been done in this 12-in. mill. Scope of the Tests A paper on fine grinding at Lake Shore Mines was published in July 1940.1 This paper covered 7 years of intensive research on fine grinding as well as sizing methods and equipment, plant scale grinding tests on 5x16-ft tube mills with and without .grate discharges-both with 1 1/4-in. and 3/4-in. balls, the use of laboratory mills to evaluate plant changes, and several reports on classifiers and classification. In the following July the addendum report' was added in which the idea of series-circuit grinding was introduced, and the results of running five stages of tube mills and bowl classifiers were shown. Since 1940, the ball milling end of the plant has been altered extensively as a result of tests on the use of 3 1/2-in. rods in 7x6-ft mills and the use of the Tyler repulping screen with from 7 to 14 mesh screens. These tests are, lengthy and may be covered in a separate 'report later. The scope of this report is confined to ore ground by rod milling and ball milling until it passed through an 8 mesh Tyler Ty-rod screen. The -8 mesh screen undersize then was pumped to a primary bowl classifier in open circuit and the sands .from the bowl sent to the primary pebble mills, see Fig: 1. In the pebble mill circuit the ore is ground to 90 pct -325 mesh (24 pct + 28 microns) In studying the flowsheet, attention should be paid to the efficiency of the classification equipment used. The Tyler repulping screen is an efficient machine on the 8 to 10 mesh separation, and the bowl classifier is equally efficient at the 325 mesh separation. Efficient classification is a necessity for series-circuit stage grinding. The ore is hard siliceous porphyry, 60 pct SiO2, 80 pct insoluble. Its grindability at different. meshes has been shown near the top of 'the list in F. C. Bond's grindability tests' Lake Shore is not shown, but an adjacent-mine with identical ore, Wright-Hargreaves, is. Reasons for the-Changeover Since 1936 grinding balls have been rising steadily in price with no sign of stopping. For a mill that used 4.5 to 5.2 lb of grinding balls for every ton of ore ground this rise represented an alarming increase in grinding costs. In many cases the quality of the grinding balls fell off as the scrap steel became more difficult to obtain. The ratio of tube mills to ball mills increased with the use of the Tyler repulping screen in the ball mill circuit. Originally only 3.0 lb of balls per ton were used in the tube mills, and this

Jan 1, 1952

By John C. Martin

The discovery of a new gas reservoir demands that the planning of a sottnd well-spacing program be initiated early in the development stage. It is the purpose of this discussion to illustrate by actual field examples the application of basic well-spacing principles, previously developed for oil reservoirs, to the problem of well spacing in natural gas fields. These studies are presented for the field use of geologists and engineers who are concerned with the initial planning of the proper development of the newly discovered gas reservoir. INTRODUCTION The phenomenal growth of a vigorous natural gas industry emphasizes the increasing importance of natural gas as a source of energy, fuel, and raw materials to our nation's economy. Since 1945 marketed production of natural gas for the U. S. has increased 21/2 times to a record high of 10.6 trillion cu ft during 1957. As major participants in the gas industry, we share an added interest to develop and produce our natural gas reserves with constantly improved efficiency. The subject of well spacing is vitally important to the gas industry, for the well itself plays a significant role in the development of the natural gas reservoir and in control of the recovery process. Maximum utilization of wells is an integral part of sound conservation practices. The discovery of a new gas reservoir demands that careful choice of well location and well spacing be made and that the planning of a sound well spacing program be initiated early an the development stage. With the drilling of the first development well, efforts of the geologist and engineer must be directed toward acquisition of adequate technical evidence upon which a firm recommendation for a spacing program may be based. With this technical appraisal as a foundation, operators and state regulatory agencies jointly can go far in providing a framework for sound development of gas fields to achieve a program of conservation that avoids the unnecessary well. WELL-SPACING CONCEPTS Through laboratory and field investigations of the mechanism of the recovery of oil and gas, of fluid behavior, and of effective control of reservoir and well, a crystallization of ideas regarding reservoir behavior has emerged as a well-developed technology. Associated with a better understanding of the fundamental principles underlying reservoir and well behavior has been the growth of concepts concerning the role of wells and their spacing in the development and operation of an oil or gas reservoir. In addition to serving as outlets for the withdrawal of fluids from the reservoir, wells are recognized as having two other important functions: (1) providing access to the reservoir to obtain information concerning the characteristics of the reservoir and its fluids, and (2) serving as a means by which the natural or induced recovery mechanism may be effectively controlled. Beyond a minimum number of wells required to fulfill these two functions, additional wells will not increase recovery. With particular emphasis upon well spacing in oil reservoirs, many studies of the well spacing-recovery relationship have evolved the concept that the ultimate oil recovery is essentially independent of the well spacing.' These fundamental concepts are no different when regarding the role of wells and their spacing in the natural gas reservoir. They are equally applicable to the consideration of well spacing in gas reservoirs. For the gas reservoir, the problem of well spacing then revolves around the question of drainage and the degree or extent to which a well may drain gas from its surrounding reservoir environment. Theoretical and Experimental Work During the past 30 years, theoretical and experimental work carried on to study the physical principles involved in the flow of fluids through porous media has shed light upon the matter of drainage. Fundamental mathematical equations have been derived to describe the mechanism of flow of oil and gas through porous rocks. With the recent advent of high-speed digital computers, attempts have been made with mounting success to develop solutions, employing numerical techniques, to mathematical expressions that describe more rigorously the physical behavior and mechanism involved in the unsteady-state flow of compressible fluids, such as a gas, through porous rock. In 1953, Bruce, Peace-man, Rachford and Ricez published a stable numerical procedure for solving the equation for production of gas at constant rate. The results of these calculations are significant with respect to this matter of drainage, for they indicated (1) that depletion of the gas reservoir resulted in a drop in pressure at the extremity of the

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By William Y. Holland, Roger H. Cook

Dexter H. Reynolds (Chapman and Wood, Mining Engineers and Consulting Geologists, Albuquerque, N. M.)—A number of questions are raised by conclusions and inferences made in the above-mentioned paper. The more troublesome of these concern use of the various pozzolans to combat the deleterious effects of the alkali-aggregate reaction. The most alkali-reactive materials listed are opal and rocks containing opaline silica. The pozzolans mentioned specifically for use as amelioratives are opaline shales and cherts. These are stated to retard the expansion caused by the alkali-aggregate reaction. Another well-recognized pozzolan is diatomaceous earth, which consists principally of opaline silica. A pozzolan presumably owes its effectiveness to its high reactivity with the alkaline liquid phase of the concrete mix. It appears reasonable to expect that finely divided opaline silica added as a pozzolan would be more susceptible to reaction with the alkalies present than would larger particles of the same material. The authors report that work with high and low alkali cements indicates that in the presence of alkali-reactive materials, deleterious expansion depends upon the alkali content of the cement. The total effect, therefore, should be more or less independent of the amount of reactive aggregate present, and still more independent of its state of subdivision. The deleterious effects should, if anything, be aggravated by the addition of a finely divided, highly reactive pozzolan. Further, if the alkali-aggregate reaction is of great importance in the long-term soundness of concrete structures, the addition of a pozzolan to a concrete made with aggregate free from known deleterious materials would be a questionable procedure. The benefits reportedly accruing from such use of pozzolans are greater ultimate strength for a given cement content, increased resistance to deterioration by exposure to sulphate solutions and other mineral waters, and greater resistance to damage by wetting and drying and freezing and thawing. In view of the deleterious effects of highly reactive materials are these benefits ephemeral? The same considerations apply to another alkali-reactive material, chalcedony, which appears to consist of ultrafine-grained quartz, with opal absent in detectable amounts. Quartz flour is notably reactive chemically and physiologically (cf. Ref. 11 of Holland and Cook's paper), a fact borne out by its effectiveness as a pozzolan, which presumably might be expected to offset the deleterious effects of the presence of chalcedony in the aggregate. A second question of some importance concerns the reportedly highly deleterious reactivity of acidic and intermediate volcanic glasses, such as rhyolite, perlite, and pumice. Air entrainment is listed as one of the ameliorative measures to combat the deleterious effects of the alkali-aggregate reaction. The alkalic-silica gel formed by the reaction may expand into air bubbles and thus not cause appreciable expansion of the concrete mass. It would appear then that pumice and perlite, particularly perlites of the pumiceous types and other types after expansion, would also tend to counteract the expansion, since these materials consist largely of voids and air bubbles. Certainly this would be expected of structural concrete in which pumice or perlite is used as total aggregate. Finely ground pumice, perlite, and volcanic ash have been demonstrated to be active pozzolans (cf. Pumice as Aggregate for Lightweight Structural Concrete by Wagner, Gay, and Reynolds, Univ. of New Mexico Publications in Engineering No. 5, Albuquerque, 1950). In fact, the term pozzolan was first associated with finely divided pumice or volcanic ash. Such materials were used with hydrated lime as the sole cementitious agent in constructing public buildings, roads, and aqueducts by the ancient Romans. The deleterious alkali reactivity of the volcanic glass, itself containing several percent of the alkalies, apparently did not contribute to the remarkable state of preservation of those ancient structures, as exemplified by the Appian Way and the Pantheon Dome. Still a third question involves .the reactivity of constituents of concrete when exposed to various salt solutions. Resistance to. deleterious expansion and cracking as a result of contact with mineral waters and its relationship to the mineral content of the aggregate are not mentioned by the authors. Yet the phenomena pictured in Fig. 1, and especially in Fig. 2, appear very much like those caused by exposure to mineral waters. The deterioration of concretes exposed to sulphate waters is generally considered related to the chemical constituency of the cement itself, particularly to the relative amount of tricalcium alum-inate contained. Could not many of the ill effects presently blamed on alkali-aggregate reaction really have been caused by contact with sulphate or other salt-containing mineral waters? Or perhaps their use as mixing waters? May not the deleterious expansion be as much a function of the chemical makeup of the cement as it is of the mineral constituency of the aggregate? Would it not be just as important to use alkali-free mixing water as it is to use a low-alkali cement? It appears obvious that resistance of cements and concretes to sulphate and other salt solutions cannot be left out of account in discussion of deterioration of concrete structures with time. This factor may be of equal or even greater importance than the alkali-aggregate reaction, particularly for concrete subjected to wetting and drying cycles, such as airstrip paving, water-retaining dams, and highway structures. Another very important factor is called to attention on page 1022 of the article in Mining Engineering, October 1953, in that failure of concrete structures may result from poor construction practices and use of too high water-cement ratios. Both of these can contribute remarkably to decreased resistance to attack by sulphate waters, and presumably could have an equally remarkable effect upon extent of damage resulting from the alkali-aggregate reaction. From the above remarks it appears that while alkali-aggregate reaction may be an important factor in decreasing the useful. life of a concrete structure, it is not the only factor involved, and it may not be even a controlling factor. Likewise, many of the phenomena apparently associated with the alkali-aggregate reaction may have resulted from cond'itions which had little relationship to the alkali-reactivity of a constituent of the aggregate. Certainly if alkali-aggregate reactivity is a major factor in bringing about early failure, one cannot help feeling anxiety concerning the future of the many concrete structures in this country and abroad in which pumice and perlite were used as total or partial aggregates. This anxiety can only be dispelled by calling to mind that among the best-preserved relics coming down to us from ancient times are structures made with mortars containing highly alkali-reactive aggregates.

Jan 1, 1955

By AIME AIME

ONE test is worth a thousand expert opinions, say the engineers of the John A. Roebling's Sons Co. of Trenton, N. J. Confronted with the job of building the cables for the new Hudson River Bridge between Fort Lee and upper Manhattan, the Roebling organization, in spite of its long and varied experience in building cables for suspension bridges of various sizes, recognized that old yardsticks would be of little value in estimating safety factors for the immense span across the Hudson.

Jan 1, 1929

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1'2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:' Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal'3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.' Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By H. L. Lovell, L. H. E. Weyher

Cyclones have been used successfully in the mineral industries to solve solid-liquid as well as solid-solid separation problems in the processing of fine particles. Substantial information is available about the operation of cyclones as thickeners, classifiers, and concentrators using a dense medium. However, very little is known about the operation of the cyclone as a fine coal concentrator not using dense medium. This application of the cyclone, namely to wash fine coal in water, requires that classification phenomena be minimized in order to arrive at an effective separation of the high density ash and sulfur-bearing mineral particles from the low density coal particles over a wide particle size range. The authors have investigated the role of feed pressure, orifice diameters, and vortex-finder length in the cyclone washing of fine coal (--1/4 in.) in water. The results of this investigation show that cyclone washing of fine coal in water is an effective unit operation particularly capable of reducing the inorganic pyritic sulfur content. The combination of hydrocyclones with complimentary equipment such as Sieve bends, shaking tables, and flotation units appears to be especially promising and may ultimately yield fine coal processing systems that could approximate the high recovery efficiencies of today's coarse coal cleaning circuits. In the future, fine coal beneficiation can be expected to receive even greater research emphasis as a result of increasing sulfur restrictions on all major coal markets. In a previous paper, work, conducted at the Pennsylvania State University, on the hydrocyclone washing of fine coal was discussed.' The initial evaluation based on that wo-rk demonstrated the feasibility of hydrocyclones as fine-coal cleaning devices, and in that previous paper selected test data were presented that showed in principle how product yield and assay respond to variations of the major cyclone operating variables. The present paper reports in greater detail on the findings and presents a comprehensive evaluation of the data as follows: (1) Hydrocyclone throughput rates were related to feed pressure and other variables by regression equations. These equations are compared with other capacity-vs.-pressure drop expressions taken from the literature on classification cyclones. (2) The flow ratio was found to be the most important variable for the separation of the solids. Control of this ratio through various cyclone operating parameters is discussed. (3) The data on the product yield as well as the ash and sulfur assays from the tests were evaluated by means of correlation and multiple regression analyses. Because size-classification phenomena cannot be suppressed completely in hydrocyclone washers, product yield and assay data are regressed against cyclone operating variables separately for different size classes. These equations then reveal how the interactions of the cyclone operating variables vary in terms of the separation for different size classes. (4) Density partitions from additional tests were analyzed by supplementing product-size analyses with sink-float analyses of the separated product size classes. The evaluation of these data show how classification phenomena affect separation by density. The results demonstrate in particular the feasibility of the hydrocyclone washer for removing pyritic sulfur from fine coal. In addition to these specific findings, the investigation points up the value, in general, of using hydrocyclone washers in combination with unit operations such as screening, table concentration, and flotation. In order to make optimum use of the hydrocyclone washers and work out the most effective combination of unit operations, it is important to have careful flowsheet analyses corresponding to the given feed and product requirements. Analyses of this kind are now possible by means of computer simulation of flowsheets and other operation research tools. INTRODUCTION Before proceeding with the detailed treatment and evaluation of our results, it will be useful to review the fundamental aspects of cyclone separators and also restate the experimental procedures and data handling employed in these studies. Review of Cyclone Fundamentals: AS shown in Fig. 1, the basic components of cyclones commonly used

Jan 1, 1970

By S. M. Marshall

FOR a number of years European investigators have used laboratory methods of predicting the probable strength of coke made from coal, and recently several investigators in the United States have reported the use of various tests for this purpose. There is at present no method accepted as standard, however, nor is there even agreement as to the general type of test that should be used. Furthermore, because the details of most of the tests have not been worked out carefully, one investigator can not hope to duplicate the work of another. The extension of coke manufacture to new localities in the United States, and the increasing need for cokes of exceptional qualities made from the most economical mixtures, made it desirable to have some simple laboratory test which will determine whether given coals, alone or blended with other coals, are more satisfactory from the standpoint of coke strength than others of different cost. The work described herein has resulted in the development of a simple laboratory test which, it is believed, can be generally adopted in coal laboratories, and which will give concordant results even though performed by different investigators in different laboratories. The general method of predicting whether a coal or a mixture of coals will produce a strong coke, resistant to crushing and shattering, has been to correlate the known strengths of the cokes produced in commercial ovens with some measurable constituent or with some property of the coals, and then to use the relationship so found for forming an estimate of the coking strengths of coals unknown. Several such correlations have utilized the percentages of the various ultimate constituents of coal, such as the oxygen content and the hydrogen-oxygen ratio;(39)§ other correlations have involved the proportion of a, (3 and y compounds, (17'21,30 or of "oil and solid bitumens."(16,30) Also a relationship has been traced between the coking properties of coal and the rate of change of the resistance offered to the flow of an inert gas by fine particles of the coal while being slowly heated. (11,17b) But the most general corre-

Jan 1, 1929

By G. A. Beske, P. Hilsch, J. Wulff

The effects of the growth precipitates on the su-perconduching properties of an Al- 15 al. pel Zu alloy have been studied using magneization, transition lem-perature, and residual resistivity measurements. Aging at 230C for 1/2 to 11 he produces an increase in Hfp, Ike field of first penetration, and tut increase in trapped flux. The upper critical field, Hc2 remains constant for such aging tunes. Aging at 200°C produces a decrease in Hfp and an increase in trapped flux. The transition temperature remains constant at Tc - 1.227° ± 0.02°K for aging at 220°C for tims of from 1/2 to 10 hr, and for aging at 200°C it remains constant at Tc. = 1.18° i 0.02°K for times from 1/2 hv to 26 hr. The observed behavior indicates that the superconducting matrix when aged at 220°C behaves tike a type U su-perconducior, but when aged at 200°C behares like a type I superconductor. The magnetization changes after aging can be attributed to the growth and clutnge in distribution of the precipitate in a matrix of fixed composition. IT has been realized for some time that the superconducting properties of alloys are highly structure-sensitive. This is evident in the work of Mould and Mapother1 who examined the properties of an aluminum alloy. Precipitation effects have also been briefly mentioned in other studies.2-4 Bonnin and coworkers5 have observed a sharp inc rease in trapped flux in an A1-Mg alloy when the residual resistivity reaches a value that indicates it is a type II superconductor. Recently Blanc, Goodman, and Nemoz5p have reported on precipitation effects in A1-Ag alloys. Detailed studies of precipitation in Pb-Sn and Pb-Cd alloys made by Livingston6 serve to show that the upper critical fields are enhanced by quenched-in solute. Furthermore. at various stages in the precipitation process? the upper critical field is determined largely by the remanent solute. The observed magnetic hysteresis and trapped flux in such alloys result from the interaction between precipitate and the flux filaments in the mixed state. The flux trapping appears to depend largely on the precipitate distribution and is greater if the superconductor is type II than if it is type I. To examine the effect of precipitation in another alloy system, particularly one in which the composition of the superconducting phase does not change significantly during the course of precipitation, the Al-Zn system seems interesting, especially in view of the transition temperature and resistivity studies of Chiou and seraphim.' Furthermore, the recent detailed electron-microscope studies of an Al-Zn alloy by Richards and Garwood8 provide a guide for relating superconducting properties to changes in structure. For these reasons, magnetization, transition temperature, and residual resistivity measurements for varying times of heat treatment at two temperatures were made with a -15 at. pct Al-Zn alloy. The results are reported in this paper. I) EXPERIMENTAL The alloy used was prepared by Cominco Products Inc. from 99.9999 A1 and 99.999 Zn. It was chill-cast, swaged, and drawn to 0.125-in.-diam rod. The analyzed composition was 15.6 at. pct Zn (31.1 wt pct). A jeweler's saw was used to cut the 0.125-in.-diam rod into the 0.875-in. lengths needed for magnetization measurements. The ends of the cylinders were slightly beveled to remove the sharp edges. A portion of the original 0.125-in.-diam rod was drawn into 0.010-in.-diam wire and used for transition temperature measurements. Specimens were suspended from wires within a vertical furnace during heat treatment. All were homogenized at 500°C for a minimum of 3 days and subsequently solutionized for times in excess of 6 hr. The solutionizing temperature was held constant to +3°C. Individual specimens were homogenized, quenched, and aged several times and no effects indicating loss of zinc were noted. The suspended specimens were quenched by cutting the wires and allowing the specimens to fall into a silicone oil bath held at the aging temperature. They were then isothermally transforked by aging in the same bath used for quenching. After aging for the required time (approximately 10 min aging was necessary before the upper critical field reached a fixed value), they were briefly (1 to 2 sec) dipped into an acetone bath at room temperature to remove adherent oil and then immediately transferred to liquid nitrogen where they remained until inserted into the helium bath (usually within an hour). The temperature of the aging bath was held constant to +3°C for longer aging times. The cryostat used for the measurement of superconducting properties consisted of outer and inner dewars for liquid nitrogen and liquid helium, Stokes 6-in. booster diffusion pump and Stokes Model 212 mechanical pump, temperature controller to measure and control the temperature of the helium bath, and a superconducting solenoid with inserted search coils to provide the magnetic field and measure the magnetic moment of the specimens. A schematic diagram of the cryostat is shown in Fig. 1. An ultimate temperature of 0.85°K was reached with this apparatus. The temperature controller used is similar to the one described by Blake and chase.' A 0.5 pct Allen-Bradley carbon resistor and a nichronle heater (200

Jan 1, 1968