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By E. J. Koval

Practical miscible displacement processes will be characterized by lingering of the solvent into the oil. The lingering process is brought on by viscosity differences, and can be accentuated by channeling and longitudinal dispersion. The effects of these factors on the efficiency of unstable completely miscible displacements are combined in what is called the K-factor method. This method, analogous to the Buckley-Leverett method, predicts recovery and solvent cut as a function of pore volumes of solvent injected. Experimental data are included and show excellent agreement with theory for a wide variety of sandstone cores and viscosity ratios. INTRODUCTION Theoretical considerations,1 laboratory experiments,2 and pilot tests3 lead to the conclusion that miscible displacements in the field will be unstable In an unstable miscible displacement, the solvent fingers through the oil. This fingering leads to early breakthrough of the solvent and an extended period during which both oil and solvent are produced. For such a system, there appear to be four principal factors which bring about or accentuate the effects of instability: longitudinal dispersion (including geometrical effects), channeling, viscosity differences and gravity differences. Other factors, such as diffusion and flooding rate, can also influence the effects of instability, but at the flooding rates considered in this report, circa 15 ft/D, they are unimportant. Longitudinal dispersion can be thought of as a spreading of the solvent front caused by the presence of microscopic inhomogeneities. Channeling of the solvent occurs when a porous medium has macroscopic inhomogeneities; i.e., gross permeability variations. Viscosity differences lead to fingering of the less viscous solvent. This difference in viscosity accelerates the growth of fingers along paths previously developed because of permeability variations. Gravity differences lead to overriding by the usually less dense solvent. Al- though gravity effects are generally small at a flooding rate of 15 ft/D, they would, nevertheless, unnecessarily complicate the interpretation of flooding experiments. For this reason, all the experiments reported herein were done with matched density fluids. Fingering and the resultant poor areal sweep were recognized early as the dominant influences on the efficiency and the economics of miscible displacement processes. Much research effort has been spent on ways to minimize fingering and increase areal sweep such as the use of graded viscosity slugs4 or water slugs. Some researchers attempted to work out ways to prevent fingering completely; i.e., to achieve a stable displacement through gravity or latitudinal dispersion stabilization. l Others did not attempt to control fingering but obtained an economic process by merely recycling the solvent and sweeping pattern by pattern.6 During this period, all aspects of fingering came under close scrutiny. Some researchers reported on how fingering looks2 and how it is affected by viscosity ratio,7 geometry,7 and slug size.2,* Peaceman and Rachfordg suggested a mathematical approach to the prediction of unstable miscible displacements in relatively homogeneous sand packs, but their work cannot be extended conveniently to heterogeneous systems. Hence for a heterogeneous system, no method is presently available for predicting solvent cut and recovery as functions of pore volumes of solvent injected. The purpose of this investigation was to attempt to fill in the gap in our knowledge concerning the prediction of performance of unstable miscible dis placements. Necessarily, the system selected for study was a relatively simple one. The restrictions placed on the system were: (1) The system was linear; (2) The solvent was miscible in all proportions with the oil in place; (3) The solvent was continuously injected into the porous medium; (4) Gravitational effects were eliminated by matching densities and (5) All the flood rates were high and constant at 15 ft/D to avoid any small rate effect and to minimize any diffusion effects. To simplify and to indicate that both longitudinal dispersion and channeling arise from permeability variations, the effects which they cause or influence have been termed heterogeneity effects. The use of

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse grained specimens of high purity aluminum in the temperature range 800' to 1150°F, permitted the formulation of a theory explaining the formation of kink bands. The X-ray Laue back-reflection technique was used in conjunction with metallographic studies to determine the crystallographic elements involved in kinking and to measure the rotations of the bands. THAT metals deform by the formation of kink bands was first shown by Orowan1 in 1942. He manually compressed cadmium single-crystal wires, the basal planes of which were parallel to the wire axis and to the direction of compression. He found that kink bands formed quite suddenly. Similar experiments were performed by Hess and Barrett2 on zinc with a hydraulic testing machine to permit slower more careful compression. They observed that kink bands formed progressively with increasing compression. Recently Washburn and Parker3 observed the formation of kink bands in zinc single-crystal specimens during tension creep experiments. Each of these authors observed the formation of kink bands but did not make a complete analyses of the crystallographic relationships. In addition to these studies on hexagonal metals, extensive investigations of kink bands formed during deformation of aluminum in tension at room temperature have been reported. Two types of deformation bands have been observed during the deformation of aluminum at room temperature. These are: 1—kink bands: these exhibit a sharp curvature of the lattice along certain surfaces, and 2—bands formed by secondary slip along certain regions. As has already been shown by Honeycombe,4 it is important to point out the difference characterizing the two types of deformation bands. In the first case. for moderate deformation, only one system of slip planes normally is active; in the second case, however, two slip systems are active in the deformation bands. The latter have a rumpled surface because of the action of the two slip systems. In the present work only the first type of band was studied and to avoid any confusion the term kink band will be used exclusively in the discussion which follows. Honeycombe' observed that very narrow kink bands (width, 0.01 mm) formed along the (110) planes during the deformation of high purity aluminum at room temperature. He observed narrower ones in commercially pure aluminum and found also that their width decreased with decreasing temperatures. Chen and Mathewson5 reported the formation of kink bands during tensile testing of single crystals of high purity aluminum at room temperature and pointed out that some rotation occurred about a [211] direction. The influence of the bending moment on the formation of kink bands was illustrated by the experiments of Rohm and Kochendorferl0 who used a Polanyi apparatus to obtain pure shear during tensile testing of high purity aluminum single crystals. Under such conditions only one slip system was active and no kink bands were observed; consequently, no noticeable asterism was detected after deformation. The influence of the bending moment will be discussed later. Calnan8 gave a detailed account of the work performed on kink bands obtained during deformation of aluminum at room temperature. Because no explanation of the process of kink band formation in creep was given in the previous investigations and because some of the above observations are vital to the following discussion the brief review of the literature has been given. It is proposed in the present work to provide an explanation of kink band formation during creep deformation at elevated temperatures. Results and Discussion Kink bands were observed to form during tensile creep testing of high purity (99.995 pct) aluminum specimens, having a very large grain size, in the temperature range 800" to 1150°F. These observations were made in grains which occupied the whole cross section of the specimen. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled to permit easier metallographic and X-ray observations. The final

Jan 1, 1954

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper' showed that the transfer obeyed first-order kinetics. The second' presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.' It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By Gerald Sherman

MINING asbestos ore by caving at Thetford Mines, Quebec, has been described in the Transactions of the Canadian Institute of Mining and Metallurgy in papers presented by the staffs of The Asbestos Corp. Ltd., in 1934, and Johnson's Co. Ltd., in 1941. The production by caving prior to 1949, in round figures, has been 14,500,000 tons of ore by The Asbestos Corp. and 5,500,000 by Johnson's Co. They are the only caving operations in asbestos at the present time. The Jeffrey mine of the Canadian Johns-Manville Co. at Asbestos, 40 miles southwest of Thetford, is well along in preparations for caving, and The Bell Asbestos Mines Ltd. at Thetford Mines, will follow their examples later. GERALD SHERMAN, Member AIME, is Consulting Engineer, Johnson's Co. and Canadian Johns-Manville Co., New York, N. Y. AIME San Francisco Meeting, Feb. 1949, and New York Meeting, Feb. 1950. TP 2828 A. Discussion (2 copies) may be sent to Transactions AIME before May 31, 1950. Manuscript received Nov. 2, 1949. Nearly all of the asbestos produced by the western hemisphere is mined in those districts of Canada. Since it has been the subject of a number of technical papers, this contribution is offered as a review of progress. Some introductory information seems appropriate, for few members of the American Institute of Mining and Metallurgical Engineers are familiar with the mineral, or how asbestos deposits differ from others in caving characteristics. Asbestos is found in peridotite, a basic intrusive rock irregularly altered to serpentine and erratically fractured, well enough to cave in bulk, but leaving many blocks of solid ore of all sizes scattered through the deposit. Chrysotile is the variety of asbestos produced in Canada. Its fibers are the most valuable commercially, having a good proportion of long fibers, strong, silky, flexible, and suitable for spinning. The fibers occur in all lengths, from the microscopic to 3 in., or more, the shorter are more abundant. Their values depend on length combined with other qualities noted above. They occur as veinlets filling fissures in the peridotite, with crystals compactly arranged in parallel across the cracks. They are sometimes lightly frozen to the walls but the partings are distinct, often marked by particles of magnetite adhering to the fiber ends. Sometimes they break away from the rock in slabs an inch or more in thickness. In wide fissures the fibers are not always continuous, the "broken fibers" being separated by lines of parting with occasional scattered grains of magnetite, which is an injurious mineral to be elirninated when possible. In addition to the chrysotile ''Cross fiber," some "slip fiber" is found in fault fractures in limited quantities of less valuable character. With the exception of the Asbestos Corp, ore, in which the content is said to be more uniform, asbestos is eccentrically distributed through the peridotite. It is the general impression that the higher grades are more often found in hard rock. There are rich pockets and leaner areas which range down through various grades to minor barren sections. Wholesale mining is necessary to make sure of recovering all the high grade for there are no reliable indications of its existence. Ore selection only appears in constructing assay-grade limits for caving. The mill yield of the Thetford ore body in 1934 was 6 to 10 pct of the ore milled, made up of all classes, with occasional runs up to 15 pct or so. Quotations for Canadian asbestos* are as follows: Per Ton No. 1 Crude (% in. and longer) $896 @ $960 No. 2 Crude (Y8 to % in.) 350 @ 545 Spinning (less than % in.) 204 @ 378 Other classes, price diminishing with length. Shorts or "refuse" 24 @ 46 • From Eng. and Min. Jnl., Nov. 1948. Asbestos of even superior quality for electric insulation is found in Arizona limestone. It is white, containing very little combined iron, but occurs only in small quantities.

Jan 1, 1951

By A. M. Gaudin

Activation of sphalerite with silver ions results from the exchange of two Ag ions for one Zn ion in the sphalerite lattice. The exchange is proportional to the logarithm of time and proceeds until either of the reactants is consumed. Sodium cyanide prevents the activation of sphalerite by controlling the ratio [Zn++]/[Ag+]' in solution. If sphalerite has already been activated with excess silver, cyanide ions can deactivate sphalerite provided oxygen is present. SOLUBLE: silver salts are effective activators for flotation of sphalerite with potassium ethyl xan-thate as collector.* Since sphalerite takes up large quantities of silver ions rapidly,2-4 investigation of this system appeared fruitful for studying the mechanism of sphalerite activation and deactivation. Experimental data presented here comprise studies of the mechanism and rates of activation and deactivation of sphalerite with silver and cyanide ions. A 20-lb sample of sphalerite from Ottawa County, Oklahoma, was handpicked, crushed, screened, hy-drosized to produce a 65/100-mesh fraction, and purified by electrostatic separation. The sphalerite was then leached with benzene and absolute ethyl alcohol to remove possible organic contaminants and with 0.1 M NaCN to remove any copper that might have been picked up during screening. The benzene had been specially purified by grinding with fine sphalerite for 12 hr to remove trace impurities that might have had a specific affinity for sphalerite. Ii'inally, the mineral was washed, dried in flowing nitrogen, and stored in large ground-glass stoppered weighing bottles under a small nitrogen pressure. The specific surface of two samples from the 65/100-mesh sphalerite stock, measured by krypton gas adsorption," was 420 cm2 per g. Compared with spheres of the same size and specific gravity, the prepared mineral had five times as much surface. Results of a wet chemical analysis and of a spectro-graphic study are given in Table I. Manganese, nickel, tin, indium, thallium, cobalt, and magnesium were not detected spectrographically. All solutions were preparid by -adding reagent-grade chemicals to conductivitv water. which had been previously saturated with the desired gases. Nitrogen and oxygen were purified, but no attempt was made to purify the laboratory air. Radioanalysis was carried out with prepurified Ag110 tracer obtained from the Oak Ridge National Laboratory. The complete decay scheme for Ae is complex. Its primary emissions are 0.09 and 0.55 mev ß rays and 1.48 mev y raysB and its half-life is believed to be 270 days. In preparation of solutions of AgNO3, the amount of Ag110 added was negligible compared to that of the inert silver. Abstraction of silver from solution by sphalerite was measured after agitation of 1.5 g sphalerite with 20 ml of solution in 50-ml pyrex flasks. All sample preparations were carried out in a dry box so that the proper atmosphere could be maintained. After the mineral had been agitated in the silver nitrate solution, an aliquot of the solution and a sample of the wet mineral were transferred to separate counting vials and weighed. The solid sample was dried and re-weighed and the activity in both vials measured by means of a scintillation counter. With scintillation counting it is possible to count y radiation from the solid and liquid, a distinct advantage over the older ß-ray counting techdiques.4 All measurements of silver activity were made using a sodium-iodide well-type scintillation counter. The amount of zinc in solution was measured colorimet-rically by the monocolor method of Sandell.7 Activation Studies Exchange Between Zinc Ions and Silver Ions During Activation: The increase of Zn++ in solution during activation with Ag+ is shown in Table 11. These data indicate a replacement of one Zn++ by two Ag+. Analysis of a separate two-month agitation test indicated that the replacement of Zn++ by Ag+ was, as expected, in the molar ratio of 2.0.

Jan 1, 1958

By C. Wachmann

The theory presented ill this paper makes possible examination of the phenomenological aspect of secondary oil recovery by alcohol flooding. Limitutions of the theory are contingent on three primary assumptions: (1) chemical equilibrium, (2) no fingering, and (5) no dispersion. The second assumption implies one-dimensional flow. In a geometric sense the theory extends the Buckley-Leverett construction to systems of two slightly miscible fluids and to systems of three components. This is made possible by considering single-phase fluids to be made up two phases, namely of an excess of one phase and a negative amount of the other phase. The procedure is discussed in the paper. The theory also permits direct determination of the relationship between the aqueous phase saturation and the concentration of water in the aqueous phase in a zone of variable composition. The velocity of planes of constant water concentration and of constant saturation can be computted likewise and the existence of saturation discontinuities inferred. Consequently the behavior of such a Zone, which may exist at some time between a displaced and a displacing fluid, May be determined. mathematical details are given in Appendices. Problems of experimental verification are pointed out on the basis of a supporting experiment. Implications of the theory and effects of violations of primary assumptions are discussed briefly. The major conclusion is that, if the primary assumptions are met, with pure alcohol and alcohol-rich .slugs piston-like displacement of oil and water is possible. INTRODUCTION The recovery of oil from porous media by alcohol displacement has been studied for several years. Extensive experimental investigations into alcohol flooding have been carried out in the laboratory although little has been done in the field. A large amount of practical information is available, the extent being indicated by the first three papers cited 1-3 and their respecrive bibliographies. This has permitted the Formulation of inferential theories. A more analytical approach in which theories are developed primarily by reasoning from known physical principles and relationships has, however, lagged behind. In fact, an analytically derived theory of alcohol displacement has not been available. The theory presented in this paper on oil and water displacement by alcohol from a porous medium is a result of the analytical approach. The theory is idealized, as certain assumptions had to be made to make the mathematics tractable and reduce complexity of argument. In particular, major assuptions concerning conditions of equilibrium, interfacial stability, longitudinal mixing, etc., led to the exclusion of fingering, for example, from all considerations. In many laboratory experiments reported in the literature fingering could not be avoided. There is, therefore, disagreement between theories based on experimental evidence available and the analytically derived theory presented here. This theory presented is based on known physical data and makes use of the Buckley-Leverett construction and its suggested extension. The mathematical derivation of the theory is given in Appendices. Three examples relevant to alcohol displacement are discussed to explain the use of this theory: (1) system of two immiscible fluids (the Buckley-Leverett case); (2) system of two slightly miscible fluids involving an extension of the Buckley-Leverett construction; and (3) system of three components, including injection of pure alcohol or alcohol-rich fluid as a special case, which involves a more general extension of the Buckley-Leverett construction. In these discussions strict assumptions were made to impose equilibrium conditions and exclude mixing and fingering. Effects of relaxing these assumptions and consequent extensions of the theory are indicated. The complexity of the alcohol displacement process makes experimental verification of the theory essential. Some relevant evidence is offered in this paper.

Jan 1, 1965

By T. G. R. Rawlins, L. E. Brosselard

Direct platinum carbon replicas have been used to study substrates prior to growth and after initial nu-cleation of the layer. Replicas have been directly stripped and correlations have been made with other replica techniques. Mechanically polished substrates are very flat with occasional areas of "dirt", which is apparently silicon. When such substrates are etched in hydrochloric acid gas, scratches and hexagonal defects (thought to be polishing compound) are revealed, together with areas of apparent redeposition. Chemically polished substrates are much less flat although much more homogeneous in appearance. Heat treat)nents have no effect. Nuclei deposited on these surfaces, using a normal silicon tetrachloride system, have been examined. Nuclei on mechanically polished subsrates occur in random areas only, whereas on chemically polished surfaces they are more uniformly distributed. THE interest in the study of thin films and now their rapidly expanding use in many fields has increased over a period of years. Much of this current interest, particularly in the field of single-crystal or epitaxial thin films, has derived its stimulus not only from possibilities for application but also from fundamental electron-microscope studies which have indicated the manner of growth of such layers from the initial nuclei.1-5 Previous work involving study of growth processes may be divided into three categories. First, vacuum deposition, primarily of metals, on a variety of substrates has been studied by electron microscopy and electron-diffraction techniques. These have shown the three-dimensional aspect of nucleation and the remarkable liquidlike behavior of the growing nuclei which coalesce to form a complete layer. More recently this work has been expanded in two ways: by growth inside the electron microscope this has obvious advantages for kinetic studies; and by growth in ultrahigh vacuum—much of this work has been done on semiconductors.8-11 It is of interest to note that metals, specifically gold deposited on rock salt, will form only polycrystalline layers in ultrahigh vacuum unless the substrate surface is contaminated.12 In general the mode of growth for vacuum-deposited semiconductor films is the same as that for metal films. The second method of growth that has been studied is that of electrodeposition.13,14 The little that has been published suggests that the mode of growth is similar to the vacuum case, except that irregularities may perturb the electric field and disturb the growth process. The third and last primary method of growing epitaxial layers is by use of chemical methods. These techniques have generated much interest and much has been published on them. Considerable electron-microscope work has been done on the defects in the layers; however comparatively little work has been undertaken on the initial nucleation and early stages of growth. Confining ourselves now exclusively to the case of silicon, Charig et a1.15 have considered the growth of silicon on silicon substrates by hydrogen reduction of trichlorosilane, and studied the films by means of replica and transmission techniques. Subsequently they have studied the same system for growth on quartz,16 and with the addition of pyrolysis of silane on quartz and alumina.17 Also Manasevit el al. have studied deposits using silane and silicon tetrachloride on sapphire.18-14 Finally, in this volume studies of deposition on beryllia and sapphire are reported. Although Revesz and Evans20 have examined complete layers, grown by means of the widely used silicon tetrachloride reaction, no detailed examination similar to that published by Charig and Joyce21 for the trichlorosilane system has been given. Therefore this investigation has examined substrate surfaces prior to growth and then nucleation on these surfaces for the silicon tetrachloride system. EXPERIMENTAL In this work the surfaces have been studied by means of standard replica techniques. Because of the very real problems associated with artifacts introduced,22 different replicas and different cleaning

Jan 1, 1967

By M. R. Tek, R. L. Nielsen

The scaling laws as formulated by Rapoport relate dynamically similar flow systems in porous media each involving two immiscible, incompressible fluids. A two-dimensional numerical technique for solving the differential equations describing systems of this type has been employed to assess the practical value of the scaling laws in light of the virtually unscalable nature of relative permeability and capillary pressure curves and boundary conditions. Two hypothetical systems — a gas reservoir subject to water drive and the laboratory scaled model of that reservoir — were investigated with emphasis placed on water coning near a production well. Comparison of the computed behavior of these par ticular systems shows that water coning in the reservoir would be more severe than one would expect from an experimental study of a laboratory model scaled within practical limits to the reservoir system. This paper also presents modifications of the scaling laws which are available for systems that can be described adequately in two-dimensional Cartesian coordinates. INTRODUCTION Present day digital computing equipment and methods of numerical analysis allow realistic and quantitative studies to be carried out for many two-phase flow systems in porous media. Before these tools became available the anticipated behavior of systems of this type could be inferred only from analytical solutions of simplified mathematical models or from experimental studies performed on laboratory models. To reproduce the behavior of a reservoir system on the laboratory scale, certain relationships must be satisfied between physical and geometric properties of the reservoir and laboratory systems. Where the reservoir fluids may be considered as two immiscible and incompressible phases, the necessary relationships have been formulated by Rapoportl and others.2-5 Rapoport's scaling laws follow from inspectional analysis of the differential equation describing phase saturation distribution in such systems. It will be recalled that these scaling laws presuppose three conditions: (1) the relative permeability curves must be identical for the model and prototype; (2) the capillary pressure curve (function of phase saturation) for the model must be linearly related to that of the prototype; and (3) boundary conditions imposed on the model must duplicate those existing at the boundaries of the prototype. These three requirements seldom if ever can be satisfied in scaling an actual reservoir to the laboratory system because: (1) The laboratory medium normally will be unconsolidated (glass beads or sand) while the reservoir usually is consolidated. Relative permeability and capillary pressure curves are usually quite different for consolidated and unconsolidated porous media. (2) The reservoir usually will be surrounded by a large aquifer which could be simulated in the laboratory only to a limited extent. (3) Wells present in the reservoir would scale to microscopic dimensions in the laboratory if geometric similarity is to be maintained. In view of these considerations, rigorous scaling of even a totally defined reservoir probably would never be possible. The purpose of this paper is to assess the practical value of the scaling laws in the light of the unscalable variables. This has been done by carrying out numerical solutions in two dimensions to the differential equations describing the flow of two immiscible, incompressible fluids in porous media for a field scale reservoir and a laboratory model of that reservoir. While both the reservoir and the laboratory model were purely fictional, each has been made as realistic and representative as possible. The field problem selected as the basis for the investigation was an inhomogeneous, layered gas reservoir initially at capillary gravitational equilibrium and subsequently produced in the presence of water drive. The laboratory model of this reservoir was designed to utilize oil and water in a glass bead pack. The numerical treatment employed was similar to that of Douglas, Peaceman and Rachford6 and it included both capillary and gravitational forces as

By E. Topanelian

In recent years considerable progress has been made in the development and application of mathematical techniques for the solution of certain problems involving economic "strategies". Such a problem might involve, for example, the scheduling of shipments of a commodity from a number of sources to a number of destinations. The object would be to schedule the shipments in a manner so as to satisfy the destination requirements and at the same time minimize the transportation costs. The solution to such a problem is not necessarily intuitively obvious. The "obvious" solution is frequently far from optimum. If the shipments are to be made from, for example, only two sources to four destinations, the optimum schedule is readily found. However, if shipments are to be made from, say, 10 sources to several hundred destinations, even a competent and experienced scheduler may spend considerable time in finding a reasonable answer. Even then he is not sure that he has the optimum solution. Furthermore, he has no way of knowing how far from optimum the answer is. Consequently, he does not know whether he should accept this solution or seek a better one. Prior to the advent of large high-speed digital computers, little more could be done with such problems because of their great size and multiplicity of possible solutions. A problem involving 20 sources and 50 destinations would require choosing, from a very large number of possible combinations, the optimum combination of 1,000 variables. The best one could do was to utilize intuition, extrapolation from past experience, and other non-exact approaches. With a high-speed computer, however, such problems can be solved providing a reasonable computational procedure (or algorithm) can be utilized. The purpose of this paper is to describe such a procedure (linear programming) and to apply this procedure to a production scheduling problem. THE RESERVOIR PROBLEM A simple reservoir model is used throughout this analysis to illustrate the use of linear programming. Even the simplest reservoir behavior problem is nonlinear in both space and time, but if the geometry is fixed for a particular study and the time variable is quantized, the resultant system may be described by linear constraints on the variable production rates. Crude oil is available from five separate sources and is delivered to a pipeline. Sources 1, 2, 3 and 4 are ideal reservoirs and therefore are subjected to reservoir flow restrictions. Source 5 is labeled "Outside Source" and crude oil from this source is assumed to be available in unlimited quantities without considering reservoir conditions. The general problem is to determine the schedule of crude oil production from five sources which, over an eight-year period and subject to certain restrictions, will result in maximum profit. "Profit" is defined to encompass all economic factors and expenses involved in producing and selling crude oil to a pipeline facility. Such economic factors are lumped to the extent that the term represents the dollars profit from one barrel of crude oil from any of the five sources entering the pipeline system. Table 1 presents the assumed profit per barrel for oil from any of the five sources over each of the four time periods. In this chart the eight years is broken into four equal intervals of two years. The selection of four time periods of two years each and the values representing the potential profit are completely arbitrary selections for the purpose of illustrating this idealized reservoir problem. In any practical application of this work a careful economic study would have to be made in order to estimate potential unit profits for time periods as far in the future as eight years. In this particular study it is assumed that all of the potential unit profits (C) are known and fixed before the production schedule is attempted. For each reservoir arbitrary values are assigned for

By F. Paredes, W. R. Holman, R. W. Crawford

The diffusion coefficient for hydrogen in the ß titanium alloy containing 13 pct V, 11 pct CY, and 3 pct A1 was measured over the temperature range 20° to 500°C. Results fit the expression: D= 1.58 x lgs exp-------==-----) cm2,sec THE diffusion coefficient for hydrogen in the metastable ß-phase titanium alloy containing 13 pct V, 11 pct Cr, and 3 pct A1 was measured as part of an investigation of the effects of hydrogen on the mechanical properties of titanium alloys. Several theories on the mechanisms of hydrogen embrittle-ment include diffusion of hydrogen at ambient temperature as an important step in the embrittling process.'-5 In hydrogen-contaminated a-ß titanium alloys, it has been postulated that the rate-controlling step may be the rate at which hydrogen diffuses from the ß phase to stress- or strain-nucleated brittle hydride platelets at the a-ß interface.' However, embrittlement of the all-ß alloy investigated in this work may proceed by a different mechanism, since this alloy can be embrittled without the formation of detectable hydride platelets.6 Troiano has suggested that in this case the mechanism of delayed failure or embrittlement is similar to that proposed for high-strength steel, i.e., repeated crack initiation caused by a decrease in bonding energy as hydrogen diffuses to points of high tri-axial stress at the root of a notch. In both types of alloy the rate of embrittlement is believed to be controlled by diffusion of hydrogen in the ß phase. Accurate hydrogen-diffusion data in the vicinity of room temperature should therefore be of some assistance in understanding the mechanisms of embrittlement in these two classes of titanium alloys. Diffusion of hydrogen in pure titanium has been studied by Wasilewski and Kehl7 at temperatures above 500°C. Their measurements on diffusion in the ß phase were extended below the ß-a transformation temperature (882°C) to approximately 600°C. This was possible because of the 8 stabilizing effect of hydrogen. No results at lower temperatures have been published and there are no data in the literature on hydrogen diffusion in the ß -phase alloy used in this program. Hydrogen diffusion in metals is generally investigated by measuring the rate of transport of hydrogen past a solid-gas interface, i.e., by absorption, permeation, or degassing-rate measurements. These methods produce accurate diffusion data when bulk diffusion is the rate-determining step in the over-all process. However, at the lower temperatures of interest in hydrogen-embrittlement studies or under conditions where surface films are present, the measured rates may be surface-controlled and the calculated diffusion coefficients will be in error. Surface effects were eliminated in the present work by using a modification of the common welded-couple technique m which two bars with uniform but different compositions are joined before the diffusion anneal." The same type of step change in the initial concentration vs distance curve was produced by electrolytically hydrogenating thin-strip specimens which had been electrically insulated over half of their length. Concentration vs distance curves were determined, after appropriate diffusion-annealing treatments, by vacuum-extraction analyses of transverse samples sheared from the strips. Diffusion coefficients were calculated by the methods of Grube.M This technique was feasible because of the large concentrations of hydrogen which can be charged into p -phase alloys without the formation of hydrides15'16 and because of the extremely low degassing rates observed when hydrogenated titanium alloys are heated in air. EXPERIMENTAL WORK The diffusion couples were cut from a 0.022-in.-thick mi ll-annealed sheet.* Strips 8 in. long by 1/2

Jan 1, 1965

By W. S. Hyler, W. L. Bruckart

The powder metallurgy and arc-cast types of wrought molybdenum stock were studied in rotating beam fatigue. Endurance ratios of unnotched specimens after 5x10 cycles were found to be 0.74 and 0.81, respectively. Fatigue notch factors (K,) of 1.36 and 2.05, respectively, were obtained on V-notched specimens having a theoretical stress-concentration factor Kt = 3.1. MOLYBDENUM and its alloys are rapidly gaining importance as engineering materials of construction for high temperature applications. AS a wrought material, molybdenum and its alloys are outstanding above 1800°F. It is necessary, however, with molybdenum to provide elevated temperature oxidation protection. This is currently being studied by a number of investigators. Thus far, there have been no published data on the fatigue behavior of molybdenum either at room temperature or at elevated temperature. The knowledge of fatigue behavior, particularly notched fatigue behavior, becomes increasingly important as the engineering importance of a material increases, especially from the design standpoint. The work described here was directed toward determination of the notched and unnotched rotating beam fatigue characteristics of molybdenum at room temperature. Also, it was desired to learn whether any difference exists between wrought molybdenum of the powder metallurgy and the are-cast types. Fabrication History of Bar Stock For this work, bar stock was procured from Climax Molybdenum Co. (are-cast type) and from Westing-house Electric Corp. (powder metallurgy type). The processing histories of these materials are listed in Table I. The first lot of are-cast molybdenum was deoxidized by aluminum additions. The second lot was deoxidized by carbon." Both lots of the powder Microstructure A microscopic examination of these materials, as received, revealed the powder metallurgy molybdenum to be free of inclusions and to be finely fibered. On the other hand, the are-cast C molybdenum possessed numerous carbide inclusions, and the arc-cast A appeared to have coarse grained fibers. These are shown in Fig. 1. Owing to the large apparent difference in fineness of fiber between the are-cast A and the powder product and are-cast C, a check was made of the recrystallized grain sizes to determine whether these differences persisted. A series of recrystallization anneals revealed mixed grain sizes in both the are-cast A and the powder product. Variations in grain diameter of as much as 50 times were found after full recrystallization at 1200°C for 30 min. There was no distinction between the two. Arc-cast C was not checked. Room Temperature Mechanical Properties Prior to subjecting the materials to fatigue tests, room temperature mechanical properties were determined. These data, together with the tensil: strength of the notched bars, data,togetherare listed in Table tensil: There were no significant differences in the tensile strengths of the two types of molybdenum. However, the powder metallurgy material was generally more ductile and yielded at a somewhat lower stress than the arc-cast material. Tensile strengths of the notched specimens indicated a slightly greater notch strengthening effect in the are-cast C than in the powder product, lot 2. Room Temperature Fatigue Properties Sample Preparation: Specimens were prepared for use in R. R. Moore rotating beam fatigue machines. These specimens had a continuous radius test section with a minimum diameter of 0.260 in. The specimens were prepared by grinding to shape and polishing to produce a smooth unworked surface. Polishing consisted of rotating a disk in the continuous radius section on which were attached, successively, emery belts of 240, 400, and 600 grit. The specimens were slowly rotated during the operation. The belt speed was high, and rotation was such that polishing scratches were longitudinal. Unnotched Fatigue Properties: Unnotched fatigue data were obtained from a number of specimens of each of the four lots of molybdenum. The results of the tests are presented in Fig. 2. From this figure,

Jan 1, 1956

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,' it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert's apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By W. B. Nelligam, J. Tittman

Refinements in radiation logging techniques during recent years have involved increasing usage of scintillation ditectors. These detectors produce voltage pulses whose heights are related to the energies of the gamma rays which initiate them. Analysis of the gamma-ray spectrum, as indicated by the pulse heights, yields information about the chemical elements composing the formations surveyed. Refined scintillation counter techniques can furnish chemical information concerning earth formations in situ, from a study of the gamma-ray spectra emitted by the formation either naturally or as a result of neutron bombardment."' Accompanying the rising interest in gamma-ray scintillation spectroscopy, there has been increased activity in the development of accelerator-type neutron sources (in contrast to encapsulated chemical-mixture sources). Such neutron generators are attractive for several reasons: (1) they greatly reduce radiation hazards to personnel; (2) there is a great reduction in contamination danger if they are lost in the hole; (3) they can produce larger neutron intensities than can conveniently available encapsulated sources; and (4) they are capable of being pulsed, thus permitting new techniques in logging. In the past, both accelerator and encapsulated neutron sources have been used by others in conjunction with scintillation-detector pulse-height analysis. The results have not been too encouraging, due to the interference among different gamma-ray spectral lines and to the fact that the gamma-ray peaks were not too clearly distinguishable above the large and ill-defined background "noise".'.' This paper is a status report on laboratory studies of a technique using a borehole accelerator as a neutron source, which gives an improved scintillation spectrum, thus permitting more accurate chemical analyses of the formations penetrated. The Schlumberger-accelerator neutron source' is presented; the origins of inelastic and of thermal-neutron, capture gamma rays are dis- cussed, and results are given for some laboratory measurements performed in borehole geometry. THE NEUTRON GENERATOR-TUBE ACCELERATOR In the attempt to develop an accelerator neutron source which would have the desirable properties outlined in the "Introduction" and which would operate satisfactorily under borehole logging conditions, a small-diameter, cylindrical, neutron generator tube has been developed. This tube utilizes the principle of accelerating deuterons (heavy hydrogen nuclei) by a high voltage so that they bombard a tritium (heavy, heavy hydrogen) target. The resulting reactions produce large numbers of neutrons of 14 Mev energy. Furthermore, the tube is permanently sealed and, thus, the use of pumping techniques in the sonde is avoided. The tube consists of a pressure control, an ion source in which the deuterons are stripped of their electrons, an accelerating gap down which the deuterons are sped by the high voltage, a secondary electron suppressor and a tritium-loaded target. Obviously, the tube requires auxiliary circuitry in a sonde for the control of the ion source, tube pressure, high voltage and other operating variables. Neutron yields, both continuous and pulsed, have been produced under simulated field conditions in the range between 1 and 10 times those conventionally used in neutron logging applications. For the experiments discussed in this paper, neutron-pulse repetition rates in the range between 500 and 5,000 pulses/sec are adequate. Furthermore, by making suitable adjustments in operating conditions, one can vary the pulse width from a minimum of several microseconds up to dc. As will be seen later, the present application to well logging does not require that one have available pulses of neutrons which are appreciably shorter than the time it takes for fast neutrons to slow down to thermal energy in water. As a consequence, much of our interest has been directed towards the operating characteristics of the tube with pulses longer than about 10 microseconds in duration. Our experience to date shows that tubes can be operated in this manner with reasonably constant, average neutron outputs.

By I. R. Dunlap, R. F. Burdyn, F. D. Patchen

The composition and properties of a new type of cementing mixture are discussed. In these compositions, API Class A or C cements are added to n stable water-in-oil emulsion instead of the crsual water. The cement disperses in the oil phase and remains out of contact with the water under normal conditions of mixing and storage. At higher temperatcrres, such as those encountered down-hole during placement, the emulsion breaks and cement hydration can then proceed. An extremely low filtration rate is obtained; the major part of the filtrate is oil. Thickening times of the mixture may be increased to meet the 18,000-ft casing cementing schedule by varying the amount of emzilsifier. As in conventional Portland cement mixtures, high-temperature strength retrogression can be overcome by addition of silica flour. Results of several field app1ication.r show that mixing presents no diffculty if emulsion blenders are used and the emulsion is prepared beforehand. INTRODUCTION Water-in-oil emulsions., in which oil is the continuous or external phase and in which water exists as discrete droplets, have for some time been used successfully in drilling muds to reduce filtration loss.1,2 Applied to cement slurries, the same results are obtained; i. e., the fluid-loss is greatly reduced. In addition, thickening times may be extended, lower densities and strengths obtained, and water-base borehole fluids more easily displaced without contamination of the cement. A low filtration rate is often a desirable property in oil well cements since loss of fluid increases placement difficulties and may also cause damage to water-sensitive producing formations.' In the casing cementing operation where the cement slurry is pumped into the narrow annulus between open hole and casing, rapid loss of fluid to a porous formation can cause the slurry to thicken and plug the annulus before the desired fill is obtained. Where a casing or a liner is cemented against a productive formation and the well completed through perforations, the fluid lost between the time the cement first contacts the formation and the time a set is obtained may invade the zone past the depth of the perforations. If the sand contains a material which will swell upon contact with cement filtrate, permanent damage may result. Previous methods for reducing the fluid-loss of cements have employed bentonite4 as an additive, usually with a lignosulfonate as a dispersant, or a derivative of some naturally occurring polymeric material such as cellulose ether." Oil emulsion cements have also been proposedv or fluid-loss reduction, but these have been of the oil-in-water type. Bentonite cements have been used most widely and have been successful in reducing incidence of premature setting of cement attributable to loss of water by filtration. It is the purpose of this paper to describe preparation and properties of a water-in-oil emulsion cement and to relate procedures followed and results obtained in several field applications. DESCRIPTION OF SYSTEM AND MECHANISMS A water-in-oil emulsion cement is prepared by adding an API Class A or C cement to a stable water-in-oil emulsion. Fig. 1 is a photomicrograph of this emulsion before addition of cement. Here the droplets are water and the surrounding medium is diesel oil. High emulsion stability is indicated by the small droplet size [1-5 microns], and by their uniformity.' To form a stable water-in-oil emulsion as illustrated, several conditions must be met. A predominantly hydrophobic emulsifier must be present in sufficient concentration to produce a strong interfacial film; initially, the phase volume ratio (the water-to-oil ratio) must be low;

By Frederic L. Kadey

Perlite, as a volcanic glass, has been recognized since the Third Century, B.C. (Langford, 1978). The precise details of discovery often become lost in antiquity, and the variations among the stories pertaining to the more recent discovery of perlite as a material of commerce are no exception. Credit in the United States is given to a dentist who, while experimenting with tooth enamels about 1941, discovered that perlite-the rock-intumesced when subjected to heat. At about the same time it is reported that the chief geologist of Silver and Barytes Ores Mining Co. attempted to put out a picnic bonfire on the shores of Milos Island, Greece by throwing beach sand on it. The ensuing pyrotechnic display immediately conjured up in that man's mind the possibility of a new use for the volcanic rock that constituted most of the island. Very little was done with this discovery either here or abroad until after World War II. Today the name perlite is applied to both the hydrated volcanic glass, generally of rhyolitic composition, and to the lightweight aggregate that is produced from the expansion of the glass after it has been crushed and sized. Petrologically, it is defined as a glassy rhyolite that has a pearly luster and concentric, onionskin parting. Occurrences of perlite are restricted to several Tertiary to Quaternary age rhyolitic belts that trend in a generally north-south direction around the world. Commercially suitable deposits generally occur as domes of several hundred feet in height, although glassy zones in welded ash-flow tuffs and others associated with dikes and sills also have been reported. Mining is by ripping and blasting from open pits. Because of weight considerations, perlite usually is shipped to the local market area for subsequent expanding. In the United States, New Mexico leads in production with Arizona, California, Nevada, Idaho, and Colorado following in approximately that order. The principal use for expanded perlite is as a lightweight insulating aggregate in cryogenics, in plaster, concrete, and in loose fill insulation. Expanded perlite is also used in horticultural applications, and after subsequent milling and classification, as a filter aid. The United States is the world's largest producer and consumer of perlite. Table 1 shows the world production of perlite and Table 2 shows the perlite mined, processed, expanded, and sold or used by producers in the United States. Geology Composition and Morphology Any discussion of perlite must take into consideration its dual nomenclature, for it is known by the same name as both the naturally occurring rock and, after processing and expansion, as the lightweight aggregate of commercial significance. In its naturally occurring form, perlite is a rhyolitic glass that contains from 2 to 5% combined water. While perlite also can occur as andesitic or dacitic glass, these latter types are of negligible commercial significance. Table 3 lists the chemical composition of a few typical perlites (Anderson, et al., 1956; Langford, 1979). What sets perlite of commercial significance apart from other volcanic glasses is the fact that under the proper conditions of preparation-crushing and sizing-it will, when rapidly introduced into a flame of sufficient temperature, expand or "pop." All of the elements of composition contribute to the expansibility of the rock. The role of the combined water, however, is the most significant because it is believed not only to produce a fluxing effect in the softening of the highly siliceous glass prior to expansion, but it is also responsible for the explosive force of expansion through volatilization during heating. The current theory of the origin of the water in perlite is now less con-

Jan 1, 1983

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By C. D. Stahl, R. Sandrea

This investigation was made to evaluate the comparative effects of the viscosity and the phase behavior of the buffer fluid in the composite solvent displacement of Bradford crude from waterflooded sandstone cores. Buffer slugs of propane, naphtha and other refined hydrocarbons exbihiting increasingly favorable viscosity ratios and decreasing solubility relationships, respectively, with Bradford crude, were used in long Berea sandstone cores. The secondary slug was isopropyl alcohol. The results indicate that higher oil recoveries are obtained for increasingly favorable phase relationships even when these are accompanied by unfavorable viscosity ratios within the range studied. Moreover, when propane is used as a buffer slug with an adverse viscosity ratio of 36, it gives higher oil recoveries than at a similar size slug of an any1 alcohol having a viscosity ratio of 1.09. The investigation was extended to the study of the effect of flooding rate on oil recovery. Residual Bradford crude was displaced from a 6-ft Berea sandstone core at rates varying from 0.3 to 30 ft/ day. The results show that as flooding rates were increased above or decreased below a minimum range of 1 to 2 ft /day, displacement efficiency increased considerably. INTRODUCTION In recent years, the alcohol slug process as a means of tertiary recovery has been the subject of many investigations. Gatlin and Slobod showed the advantages of the combination solvent slugs over the previous single-slug process.1 The combination slugs require less total slug material to obtain similar oil recoveries. The basic combination process involves injecting a primary or buffer solvent which is preferentially oleophilic, followed in turn by a water-driven slug of isopropyl alcohol. This procedure ensures that the buffer slug, which is miscible only with the reservoir oil, displaces and replaces the oil and is in turn displaced, together with the water, by the isopropyl alcohol slug miscible with both fluids. Likewise, for those reservoir oils that show some degree of phase incompatibility with isopropyl alcohol, as does Bradford crude, a proper buffer solvent can artificially make the alcohol process technically feasible. From an economic standpoint, propane or LPG would be the most appropriate primary solvent to be used in the field; however, Taber, et a12 have indicated that the alcohol process becomes highly inefficient in the displacement of light hydrocarbons because of the entrapment of these hydrocarbons during the stabilized bank formation. Moreover, since materials such as propane have such low viscosities, adverse viscosity ratios with most reservoir oils would be penerated, thereby possibly further reducing the efficiency of the buffer solvent. This paper presents the results of an experimental study of the comparative effects of viscosity ratio and phase relationships on the displacement efficiency of Bradford crude by means of dual solvents. The work was extended to include the effect of flooding rate on oil recovery. Rates within the range of field and laboratory values were used. EXPERIMENTAL PROCEDURE APPARATUS The porous media used in this study consisted of two 10-ft and one 6-ft Berea sandstone cores, 3-in. in diameter. These were cast in galvanized steel pipe of 31/2-in. ID and the annulus was filled with Armstrong cement. The 10-ft cores were assembled by connecting two 5-ft units, which were joined together by 8-in. steel flanges fitted to the pipe. Intimate contact between the two sections was obtained by inserting a thin disk of the same sandstone between the core faces. The outlet and inlet ends of the cores were covered with threaded pipe caps. The injected fluid was gravity fed to two variable-rate positive-displacement pumps. The fluids were filtered before entering the core and the effluent was collected in an automatic fraction collector and

Jan 1, 1966

By C. H. Li, R. J. Stokes, T. L. Johnston

The phenomenon of solid-solution strengthening has previously been studied in a number of binary alloy systems.1-8 There has been, however, very little information published concerning the strengthening effects of specific solutes in magnesium alloys. Schmid and his coworkers9,10 investigated the behavior of aluminum and zinc in binary and ternary magnesium-alloy single crystals, but this work was done before high-purity materials were readily available. Workers at the Dow Chemical companyH reported increases in the critical resolved shear stress upon alloying magnesium single crystals with zinc and indium. Recently, Hardie and parkins* investigated the extent of hardening produced by the addition of various solutes to poly crystalline magnesium. The present work was undertaken to provide data on the strengthening effects of a number of solutes in high-purity magnesium, for the purpose of supplying further experimental information which might be useful in describing a general mechanism for solid-solution strengthening. To simplify interpretation of the results, the mode of deformation was limited to basal slip, through the use of single crystals. EXPERIMENTAL PROCEDURE Magnesium and magnesium binary-alloy single crystals containing indium, cadmium, thallium, aluminum, and zinc were prepared in the form of l/2-in.-diam rods, approximately 8 in. long, using a modified Bridgman technique in which the crystals were slowly cooled from the melt in a steep temperature gradient, in an atmosphere of helium. It was found that a solid-liquid interface travel speed of about 0.7 in. per hr consistently produced single crystals. The poly crystalline starting materials for the preparation of single crystals consisted of 1/2-in.-diam extruded rods, prealloyed to the desired composition. The unalloyed magnesium and magnesium-indium extrusions were furnished by the Dow Chemical Co. The other alloys were prepared at the Rensselaer Polytechnic Institute Metallurgical Laboratories. Some preliminary studies of the strengthening effect of indium were conducted at room temperature using a constant rate of tensile loading of 1040 g per min. Stress was applied to the crystals by means of a simple 5:l lever arm. The lever was loaded by a constant rate of flow of shot into a receptacle suspended from the long arm of the lever. Plastic flow was detected by an electrical resistance strain gage cemented to the surface of the crystal normal to the minor axis of the predicted glide ellipse. The crystals were acid machined to produce tensile specimens with a reduced section between the grip ends, with an additional step in the center of the reduced section to compensate approximately for the slip-retarding effect of the strain gage. The balance of the single crystals were extended in an Instron tensile tester. This machine employs a synchronously driven screw and automatically records applied load as a function of cross-head separation. It became unnecessary therefore, to employ a strain gage to detect deformation or to acid machine a reduced section. Preparation for testing reduced merely to chemical cleaning of the surface, thus minimizing the amount of handling and probability of accidental damage to the crystals. The rate of elongation employed in all the tests was 0.002 in. per min, corresponding to a strain rate of approximately 0.0004 per min. EXPERIMENTAL RESULTS The investigation confirmed the finding of many workers that the yield strength of hexagonal metal crystals is strongly orientation-dependent. This is illustrated in Fig. 1, in which o, the tensile stress required to produce gross plastic flow in eleven unalloyed magnesium crystals stressed at a constant rate of loading is plotted as a function of sin X, cos Ao where X, is the angle between the

Jan 1, 1960

By Jack White

MUFULIRA Copper Mines, Limited, conducted tests on the concentrator in 1942 to determine which type of ball mill, that is, Conical Trunnion overflow or Cylindrical Grate discharge, produced the greater quantity of finished product at the lowest cost. All the data which follows applies to Mufulira ore and to the particular degree of grinding produced with the classifiers installed at Mufulira concentrator. JACK WHITE, Member AIME, is Concentrator Superzntendent, Mufulira Copper Mines, Ltd., Mufulira, Nortltern Rhodesia. Sun Francisco Meeting, February 1949. TP 2729 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Feb. 28, 1949. Test Procedure: The test was carried out using ball mills No. 1 to 9 (conical trunnion overflow) as the standard with which to compare No. 10 (cylindrical grate discharge mill). The conical trunnion overflow ball mills are 10 ft diam by 72 in., and the cylindrical grate discharge mill is a No. 99. Each mill runs in closed circuit with a Dorr type DSFX classifier 8 ft wide by 30 ft long. The feed is considered as being identical to all ten units. The figures for the test were derived as follows. Dry Tons Milled: For No. 10 unit (cylindrical grate discharge mill) this figure was taken from the ball mill weightometer, which was corrected for error, and then for moisture content. The weightorneter was checked twice a week during the test, and the error did not exceed 3 pct at any time. The moisture was obtained from a 24 hr moisture sample taken by the ball mill operator hourly, and placed in a closed bucket. The sample was cut where the conveyor drops the feed into the ball mill chute. The Mill Sampling Department made a daily moisture determination on this sample. To obtain the dry tons on units No. 1 to 9 the No. 10 figure was deducted from the month's dry tons milled figure, which, in turn, was taken from the crusher weightometer tons corrected for weightometer error and moisture. All tons reported in this test are short tons of 2000 lb. Ball Mill Hours: This was taken daily from the Shift Boss reports giving actual running hours for each unit. Screen Analyses: Coarse Heads (Ball Mill Feed): The monthly composite coarse heads screen analysis, done by the Mill Sampling Department, was used for the minus 200 mesh in the feed to the mills. F. X. Classifier Overflow: The ball mill operators took an hourly 24 hr sample of the overflows of units No. 1 to 9. This was a hand sample, but cut with a special cutter, and is believed to be very reliable. On No. 10 unit, an hourly 24 hr sample, and an hourly shift sample were cut in the same way. These five samples were split, filtered, and dried by the Research Department and were then wet screened on a 200 mesh screen. The average of the three shifts samples on No. 10 unit had to check the 24 hr sample within 1.5 pct to be acceptable. A weighted composite was cut each day from both 24 hr samples, and at the end of each month it was screened as follows: Wet screened through 325 mesh, the plus 325 then screened on a rotap for 15 min through 65, 100, 150, 200, and 325. This was done in duplicate. All splitting, drying, and screening of samples was done by one of the Mill Research staff, to insure accuracy. F. X. Classifier Overflow Densities: These were taken from the Shift Boss reports. Densities were taken by the ball mill operator every hour. Circulating Loads: These were taken a number of times during the test both by direct method (weighing a measured portion of classifier rake sand, and deducting moisture) and by calculation using the formula:

Jan 1, 1951

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951