Search Documents

INTRODUCTION Mineral explorationists range throughout the world looking for mineral deposits which can subsequently be made into mines. Mines are not found! Mines are made, usually at great cost and not often without significant risk. The process of making a mineral deposit into a mine involves a great deal more than a complete appraisal of the deposit. The making of a mine demands detailed feasibility studies of many factors, any one of which, if shown to be negative, could prevent the deposit from becoming a successful mine. Total feasibility analysis involves at least three major fields of study: (1) economic analysis, (2) financial analysis, and (3) political and environmental analysis. Economic analysis is essential for proper decision making at many stages in the evaluation of a mineral deposit. It is the yardstick by which the proposed mining project and alter- native investment opportunities are measured. Economic analysis is concerned with costs and potential profits and can be applied at various stages in the evaluation of a mineral deposit to determine if the project merits the additional funds necessary to bring about each succeeding stage. The nearer any deposit approaches to becoming a mine, the more carefully the economic analysis should be made. Financial analysis has reference to how, where, and at what cost the investment funds can be obtained to finance the proposed mine project. Political and environmental analysis has reference to the many intangible factors that can affect the making of a successful mine. These factors loom larger today than ever before, due to the profusion of government regulations and various environmental constraints now imposed upon the mineral industry both by law and by the weight of public opinion. Ultimately, many of these intangible factors can be resolved back into the economic analysis as an added cost to mine development, but more and more often they have become insurmountable obstacles to any development of certain deposits. The role of financial analysis and the analysis of intangible factors must never be underestimated when making a feasibility study upon which to base investment decisions; however, the emphasis of this text will be upon economic factors. THE PARAMETERS OF MINERAL ECONOMIC ANALYSIS The two major elements of economic analysis are: 1) The potential earnings or annual generated cash flow of the project. 2) The investment costs necessary to realize such earnings. If the difference between the two elements is large enough, i.e., if the return on investment from the cash flow is high enough to attract investors, the project can be said to be financially feasible. The mineral economic analysis must take into consideration many parameters, some of which are known or knowable within certain limits, and others of which are unknown or unpredictable within certain limits and for which estimates must be made. Because both known and estimated parameters enter into the same analytical computations, it is important for the analyst to realize the nature of each when considering the results of an analysis. Some parameters such as the grade of mining block, although estimated, are said to be known within mathematically defined limits. Other parameters, such as the future price for minerals produced, etc., can only be estimated or "guestimated" within reasonable limits for which no precision can be assigned. Known or Knowable Mineral Economic Parameters Known or knowable parameters are: 1) Tonnage and grade of valuable minerals for the total mineral body and for individual mining blocks. 2) Metallurgical recovery of valuable mineral. 3) Minimum operating life of mineral de- posit at any specified production rate. 4) Royalty schedule, property payments, etc. 5) Sales-purchasing agreements, smelter schedules, marketing contracts, etc.

Jan 1, 1980

By H. C. H. Darley

Particles of montmorillonite-type clays consist of plate-like clay crystals stacked face to face. Under certain conditions in a suspension, these particles disperse to individual platelets with the formation of diffuse double layers round each platelet. This action has a profound influence on the rheo-logical and other properties of the suspension. This paper describes a test for degree of dispersion and uses this test to correlate changes in dispersion with changes in viscosity and gel strength. The test is of practical value in determining and controlling dispersion in drilling muds. INTRODUCTION It has long been recognized that the hydration and dispersion of clays, particularly those of the montmoril-loilite type, strongly influences the rheological and other properties of drilling muds, but little has been done to measure either of these phenomena under conditions that exist in drilling muds. The hydration of clays as such has been extensively studied by those interested in clay mineralogy, but in drilling muds it is to be expected that dispersion is at least as important a factor as hydration because of the much higher water-to-clay ratios and the very high degree of mechanical agitation. The term dispersion as generally applied to colloidal systems means the subdivision of large particles to small. Particles of montmorillonitic clays, however, consist of plate-like particles stacked face to face. Dispersion of these aggregates to individual platelets may be expected to have an unusually large influence on the properties of the suspension because of the shape factor, the enormous increase in specific surface, and the pronounced surface phenomena exhibited by the crystal surfaces. It is this form of dispersion that is particularly considered in this paper, -and the term degree of dispersion is used to imply the number of platelets per particle. The term aggregation is used to denote the opposite of dispersion, the association of individual platelets face to face to form stacks. It is important, as Garrison' has pointed out, to distinguish between the deflocculation-flocculation phenomenon and the dispersion-aggregation phenomenon. Flocculation of clay suspensions is characterized by the formation of voluminous sediments that are stable under quite high centrifugal fields. This indicates an edge to plate association of particles to form an open network type of structure, which obviously will have quite a different influence on the properties of the suspension than aggregation of the platelets face to face. The work described in this paper was primarily concerned with developing a test for degree of dispersion in clay suspensions and by means of this test to follow changes of dispersion brought about by addition of electrolytes and to show the influence of dispersion on the rheological properties. The Clay-Volume Test This test is based on the assumption that the greater the number of particles per unit weight of clay in a suspension the greater will be the volume of sediment when it is flocculated under standard conditions and centrifuged. After considerable experimentation the following procedure was established: 1 cc of the test mud vigorously shaken with 100 cc of 1-N NaCl in an ASTM oil centrifuge tube and centrifuged for five minutes in an International No. 2 centrifuge at 2,000 rpm. When drilling fluids of different solids content are being compared, the clay volume is expressed in cc per gram of clay solids, but generally changes in dispersion in a given mud are being compared and it is more convenient to report as cc of sediment. The test is strictly a comparative test, so that it is not necessary to adhere to the conditions specified above, e.g., with field muds a stronger flocculant such as Al2(SO4)3 may be preferable to NaCl.

Jan 1, 1958

By S. R. B. Cooke, Y. S. Kim, I. Iwasaki

lron oxides or the gangue minerals of iron ores can be made to float, depending upon the choice of collector. The selectivity of the separation is controlled by the accompanying chemical and operating conditions. In this report the findings on the general flotation characteristics of magnetite are summarized and the results are compared with those obtained for other iron oxides. Depending upon the choice of collector, either the iron oxides or the gangue minerals of iron ores can be made to float, the selectivity of the separation being controlled by the accompanying chemical and operating conditions. The mechanism by which a collector exerts preferential affinity for either group of minerals has been a subject of extended discussion. Previous investigations on the electrokinetic properties and flotation characteristics of hematite,' goethite,2 and quartz3 have demonstrated the electrical nature of the interaction of the collector with these oxide surfaces; anionic collectors are effective on positively charged surfaces and cationic collectors on negatively charged surfaces. Thus, from the differences in the electrokinetic properties of the above-named oxides, a theoretical basis has been provided for their separation by some typical collectors. Examination of the results reported for hematite and goethite shows that their electrokinetic properties and flotation characteristics are remarkably similar. It is of considerable interest, therefore, to examine similar information for magnetite, another common iron oxide, in order to consolidate the flotation characteristics of the three principal minerals of oxide iron ores. Such information is practically significant in the up-grading of both natural and artificial mag- netite produced from taconite, and in the treatment of partially oxidized magnetite ores. Information on maghemite and lepidocrocite, polymorphs of hematite, and goethite, respectively, is also of some theoretical interest in ascertaining the effects of crystal structure and of hydration in the iron oxide group. This article reports the findings on the general flotation characttxistics of magnetite, and compares the results with those obtained for other iron oxides. Experimentally, tlhe surface properties of magnetite were investigated by electrophoresis, and by measurement of the aclsorption of some typical flotation collectors. Its flotation behavior was tested by contact angle measurements and by simple flotation tests using a modified Hallimond tube. The basic information thus gathered was shown to be directly applicable to the interpretation of the results of batch flotation tests made on an artificial mixture of magnetite and quartz. EXPERIMENTAL MATERIALS Magnetite: Magnetite concentrate from Port Henry, N. Y., was further purified by fine crushing and magnetic separaiion, and was used throughout this investigation. For flotation tests the 150/200 mesh fraction was iso1ated and was cleaned by leaching briefly with warn 0.1 N HC1 followed by repeated washing with demineralized water. The final sample analyzed 71.71 pct Fe, 22.37 pct Fe" and 0.47 pct insoluble, and was stored in demineralized water. For e1ectrophoresis and adsorption measurements, the —400 mesh fraction of the magnetite concentrate was ground dry in a pebble mill. The surface area of the ground sample, as determined by the gas permeability method, was 70,000 sq cm per g. Since artificial magnetite has been reported to possess somewhat different physical properties than those of natural magnetite, it also was briefly examined. Preliminary flotation tests on a sample of artificial magnelite, prepared by reducing Brazilian hematite in a C0/CO2 mixture and analyzing 71.94 pct Fe and 23.78 pct Fe'', gave, however, nearly identical results with those using natural magnetite. It was concluded that artificial magnetite behaves similarly to natural magnetite. Samples which had been magnetically separated showed a tendency to cluster together due to residual

Jan 1, 1962

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By Edgar F. Cruft

INTRODUCTION It is sometimes said that "mines are made, and not found." I rather doubt that the exploration geologist would be overly sympathetic to that statement, and, of course, like most one-liners it is only partly true. Access to different financial markets are important at the mineral prospect stage. The modern mine financier has a much more complex, and interesting, job than the financiers of an earlier era, for example, the Canadian financiers of the 40's and 50's who had one simple set of options; i.e. float a company, promote it, and sell an equity stock issue, and then promote it some more. QUALITIES OF A FINANCIER Because technical people are seldom taught financing in their basic training, and because they are usually not involved in it until at quite a senior level in their careers, the whole field often acquires a certain mystique. The engineering professions have too often believed financing is the province of the accountant or financial executive and just as we in the technical world are often too quick to bristle if the latter try to tread on our domain, the opposite can just as easily be true. Unfortunately, this is another example of a compartmentalized individual, and that is one thing the successful financier cannot be. However, to be a successful financier one does not need extensive training or experience in accounting or finance. In fact it can sometimes be a disadvantage to get too buried in working only from the standpoint of discounted cash-flow analyses, ROI's, etc. It must be stressed, however, that one had better know how these analyses are made, and be knowledgeable in understanding a balance sheet, and have a good understanding of financial terminology. The difference between a simple project-type debt financing with a commercial bank and a more inventive and creative financial package comes from an intuition and an experience relating to risk-reward factors. The most important element is "common-sense", based on knowledge and experience. The goal is structure a financial package that fits the project, and in so doing it is important to recognize that it must fit within the limitations of the group supplying the money. I find insensitivity to recognize these constraints the most common mistake made in the field. Put yourself in the other person's place and understand his sources of funds and financing limitations. The engineer has an advantage in financing, as he or she has (or should have) a better idea than anyone of the value of the product, be it the mine, prospect, or company i.e. the intangible or potential worth which cannot be put on a pro-forma. He also knows, or should know, the risks involved. Two projects might look the same on paper, but a good financier must have a sense of when to take whatever deal he can get, and when to hold out based on his evaluation of future developments. It is essential to have a good sense of commodity values and trends, trends affecting the general economy (money supply, interest rates, effects of energy costs, etc.), and political considerations. He must also have a good understanding of the science and art of taxation as deals can often be financed using the government as a silent and unwitting partner by proper use of the tax laws. WHEN TO SEEK FINANCE The first critical decision to make in financing a mineral prospect is "when". At the exploration level, when it is only a dream in the geologist's eye, the alternatives are more limited than when it is a fully-engineered project. The "when" decision depends on how much in internal funds the company has to play with, and how desirable it is to invite financial participation to spread the risk. Assuming that decision is not taken out of lack of money, no one can categorically say when to do it. There is

Jan 1, 1985

By U. Andres

U. Andres (The Technion, Haifa, Israel)-The authors are to be congratulated on their research, new and interesting, in a field which, however, the present writer and his assistants have been trying since 1962 to bring to the attention of the scientific and technical world, by means of publications covering several different aspects of this many-sided problem. We announced, in these publications, the results of magneto-hydrostatic (MHD) separation of magnetic and nonmagnetic minerals which we made in magnetic fluids (in paramagnetic solutions and suspensions of magnetic particles) which interact with permanent" and impermanent" inhomogeneous magnetic fields. There is no doubt that the authors have succeeded in creating ferrimagnetic colloids made by dispergation of 10-30 wt % of magnetite in kerosene in the presence of 7-10 vl % oleic acid. It may be judged by [Figs. 3 and 4] that the suspensions represent great stability systems and also "hysteresisless" fluids [(Fig. 5)] which bear witness to the existence of superparamagnetic suspensions. If the viscosity of these colloids is not so high, and the cost of preparing them can be covered, the fluids which have here been received can possibly be of interest to the technology of mineral separation. The potential possibility and technological perspective of similar media is demonstrated in our joint work with G. Bunin18 in 1965. The research carried out on the pushing out of cylinders and spheres from magnetic fluid is impressive; it would, however, have been interesting if the authors had compared their results with those on the pushing out of bodies from magnetic fluids adduced from our work." In my books" there happens to be described an experiment on the pushing out of a sphere in magnetic wedge field, in which the pushing out force of suspension with 5 vl % of magnetite reached 125 g per cc. This testifies to interesting possibilities of these media. Our works' shows also, on the basis of Laplace's equation the receiving of an interesting distribution of pushing out forces by selection of corresponding configurations of magnetic poles. Objection must be made to the authors' introduction of the term "antigravity force." The direction of this force does not depend on the direction of the gravity force and their opposition, i.e., antigravity is only one particular case. I am in full agreement with the authors' statement that magnetic pushing out forces "can be utilized to separate nonmagnetic objects according to variations in their densities." It is, however, necessary to make only one important addition, which can be found in our research on MHS at the Technion in Haifa, namely, that magnetic fluids in magnetic fields can be utilized in the separation of minerals according to variations in their magnetic susceptibility. The authors' conclusion is especially important considering the fact that in our publications" (including one in English") some designs of MHS separators and some technological results received on MHS-separators have already been described. S. E. Khalafalla and G. W. Reimers (Authors' Reply)We were aware (mostly through Chemical Abstracts of the American Chemical Society) of the use of solutions of paramagnetic salts such as manganous sulfate in agnetohydrodynamic separations by the Russian school headed by G. Bunin."n Professor Andres' contributions to this school are also evident in his application of the ponderomotive forces in an electrolyte placed in electric and magnetic cross-fields to separate coal and other useful minerals." It must be realized, however, that the foregoing research by Bunin et al." involved the use of magnetic fields and field gradients of very large magnitudes, i.e., such that H • grad H - 101 Oe2 per cm. The magnetization of paramagnetic salt solutions range from 0.1 to 0.5 gauss (at fields of a few thousand Oersteds) and never reach saturation. The magnetization of our superparamagnetic ferrofluids ranges from 100 to 500 gauss and reach saturation at fields of a few hundred Oersteds. Hence, to effect the same separation, the quantity "H

Jan 1, 1974

By W. B. Mather

Of the 61 dikes examined some yielded cassiterite, tantalite, and beryl; eight contained spodumene; and six carried amblygonite. Two mines stockpiled spodumene as a byproduct. Only zoned pegmatite dikes carried lithium minerals. GEOLOGICAL studies have revealed the occurrence of hundreds of pegmatite dikes in northeast Brazil, Fig. I, in the three states of Rio Grande do Norte, Paraiba, and Ceara. Heretofore data have not been available on the possible production of lithium minerals from these areas, and in March, April, and May 1953 the author undertook a reconnaissance survey covering a cross-section of the pegmatite~. Sixty-one pegmatites were examined. The pegmatites of Rio Grande do Norte and Paraiba are located in an arid region (Seratao), and except in the most southerly portion there is a minimum of vegetation and overburden. The region is easily prospected and relatively accessible by jeep or truck. The pegmatites examined in Ceara are in an area of lush vegetation along the flanks of the Jaqueribe River valley. It is therefore more difficult to prospect, and the dirt roads, as a means of access, leave much to be desired. For all practical purposes rail transportation, except in Ceara, is not available. The rocks of the area are composed of Pre-Cambrian schist, gneiss, quartzite, and marbles. They have been intruded by granites, monzonites, and diorites and cut by quartz veins and pegmatites. Pre-Cretaceous erosion reduced the area to a peneplain upon which Cretaceous or younger sandstones were deposited. Recent erosion has left only a few remnants of these younger rocks. In most of the Rio Grande do Norte-Paraiba area the pegmatites were more resistant to erosion than the enclosing schists and therefore stand out in relief. This is not true in the rolling country of Ceara, where the pegmatites lack topographic expression. With regard to structure and lithology, the pegmatite~ of northeast Brazil are divided into two types, uniform and zoned. Of the 61 examined, 19 belong to the uniform and 42 to the zoned type. Uniform pegmatites are normally long, narrow, and tabular, with sharp contacts. They are composed of an intimate mixture of feldspar (microcline or ortho-clase), mica (biotite, phlogopite, or muscovite), and quartz. The grain size5 varies from fine at the contact to coarser in the interior. They are not considered a commercial source of pegmatite minerals, although efforts have been made to produce green beryl of gem variety. This type of dike is often abundant in schists and gneisses close to granite intrusives. The productive dikes — lenticular, pod-shaped, or irregular in outline, with sharp contacts — are of the zoned variety. Zone contacts are gradational, except for those with the quartz core. Zones re identified as follows, see also Fig. 3. Border Zone: This outer zone, in contact with the country rock, is composed chiefly of fine-grained muscovite and biotite, with lesser quantities of finegrained microline and quartz. It is the narrowest zone, usually measurable in inches. Wall Zone: Lying between the border and intermediate zones, the wall zone is composed of medium-grained feldspar (often microcline), muscovite, and quartz. Usually it is the widest zone. Widths of 50 ft were noted. Intermediate Zone: Lying between the wall zone and core, the intermediate zone is composed principally of coarse-grained microcline (occasionally with some orthoclase and albite). It may also carry minor amounts of coarse-grained quartz and fine to medium-grained mica. The width varies from less than 3 ft to more than 30 ft. Core: The center of the dike is composed almost entirely of massive quartz, occasionally with minor amounts of fine-grained muscovite. The width reaches 30 ft. Lithium and other minerals of potential economic value are found in the following zones:

Jan 1, 1955

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By R. M. Goldhoff, J. W. Spretnak

IN connection with establishing the mechanism by which boron enhances the hardenability of heat treatable steels, this research work has been undertaken. Spretnak and Speiser1,2 indicated the need for studying high temperature effects in boron steels and, chief among these, the possible nonhomogeneous distribution of boron in iron grains. The occurrence of this effect may be of significance in explaining the mechanism of enhancement of hardenability by boron as well as in explaining some of the observed characteristics of boron steel behavior. Primarily, then, this work was undertaken a) to establish whether or not boron is adsorbed in ? solid solutions, b) to determine the nature of any such adsorption effects, i.e., whether it is positive or negative as well as its temperature coefficient, and c) to establish the magnitude of any such effect. While past literature on this specific subject is rather sparse, a number of authors have postulated that the observed temporary loss of hardenability as well as the occurrence of the characteristic boron constituent in these steels is due to the nonuniform distribution of boron in austenite.3-0 Experimental Techniques Attempts to obtain direct evidence of grain boundary effects in boron steels have been unsuccessful, both by using the technique of Chalmers' in which small concentrations of solute made radioactive by irradiation are detected by autoradiographic means, and by means of studying cleavage fractures with the electron microscope.8 The present study attempts the design of experiments to measure the effect of boron on properties which might be subject to variation because of grain boundary effects. A study of the theoretical aspects of grain growth indicates that such studies may be pertinent. Another valid type of experiment involves the measurement in polycrystalline materials of properties whose values depend on the bulk of the grain, being negligibly influenced by grain boundaries. One such property is the lattice parameter measured by X-ray diffraction. The value of the lattice parameter reflects the average conditions which obtain over a relatively large number of atoms in a fixed crystalline lattice, and is therefore mainly dependent on bulk grain material. Measurement of lattice parameter variation over the austenite range of temperature in iron with and without boron should give evidence of concentration variations in the bulk grain material if adsorption effects are significant. Finally, use is made of the Grange and Garvey3 metallographic test for boron in which a characteristic boron constituent can be developed in austenite grain boundaries. The very occurrence of this phenomenon suggests grain boundary enrichment of boron and a study of the occurrence of this constituent and its varation with austenitizing temperature should help to detect grain boundary effects. Materials One lb ingots of pure iron, an Fe-B alloy, an Fe-C alloy, and an Fe-C-B alloy were prepared. The melting technique included an initial melting of electrolytic iron under vacuum followed by remelting under hydrogen and, finally, by melting under argon with the addition of alloying elements. Each ingot was surface machined between meltings. A quantitative spectrographic analysis was obtained on the pure ingot and, in addition, oxygen, nitrogen, and carbon were determined by the vacuum fusion method. The results of these analyses are given in Table I. Semiquantitative spectrographic analyses were performed on the alloy ingots, while quantitative determinations of the alloy additions were obtained. These analyses are shown in Table 11. The cast ingots were subjected to the following sequence of fabrication treatments: forging to 5/8 in. bars, swaging to 0.300 in. rounds, drawing to 0.025 and 0.010 in. wire. Portions of each ingot were retained in the swaged condition for experimental use. For certain portions of the work typical commercial steels were used. These materials were supplied by the Republic Steel Corp., Canton, Ohio, and correspond to AISI 8640 and AISI 86B40 compositions.

Jan 1, 1958

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 H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler') have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,' concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina' crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By L. W. Holm, A. K. Csaszar

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By G. T. Pruitt, T. L. Irby, P. B. Crawford, H. Ferrell

In water flooding peripheral, center-to-edge, line-drive or water-encroachment patterns the question has arisen, "when should a producing well be converted to a water-injection well?". It is realized that, if the producing well is shut in when water breakthrough occurs, some oil could be left in an unswept area. Yet, operation to high water-oil ratios may require processing much additional water. If a well is shut in, "where should the allowable be transferred?". A review of the literature indicates that very few data are available to the engineer to assist him in answering these questions. It is the purpose of this paper to present information which may be of value in selecting the flooding technique and the injection and producing wells and in scheduling injection and production rates. Certain phases of these problems can be studied in the laboratory. The Potentiometric model is well suited for studying many waterflooding problems. This model assumes that steady-state flow exists, that the mobility ratio is equal to one and that gravitational effects are neglected.'-' The three-phase sand model also has been recognized as an effective means for studying certain reservoir problems. Both models were used in making the study reported here. This paper discusses seven cases utilizing various waterflooding techniques. Data for the first five cases were obtained on the potentiometric model. Data for Cases VI and VII were obtained by constructing and flooding an unconsolidated sand pack (a three-fluid-phase system) and by determining the swept area and cumulative oil recovery for various types of operations. APPARATUS AND PROCEDURE The potentiometric model reservoir was 30 in. long X 10 in. wide by about 1/2 in. deep. Four wells were equally spaced in a line array along the lateral center line. (See Fig. 1.) Well No. 1 initially was an injection well for each of the patterns reported. The cases studied with the potentiometric model and sand model are described herein. The laboratory sand model reservoir was a 30- 10-in. rectangular Lucite vessel packed with sand to a depth of about 0.65 in. Four wells were equally spaced in a line array along the lateral center line. The reservoir material was an unconsolidated sand into which the reservoir fluids were mixed to yield fluid saturations of 55 per cent oil, 25 per cent water and 20 per cent gas. The water was added to the sand and the material mixed, after which the oil was added. Kerosene and water, the fluids used, gave a viscosity ratio of 1.64:1. In packing the reservoir, care was taken to assure constant fluid saturations and constant porosities. A new mixture was prepared for each run. During water flooding, a colored water was injected by a constant rate pump. The injection rate was 1.1 B/D/ft of sand thickness. For this series of tests, each of the producing wells was open to the atmosphere and, as in the potentiometric model study, Well No. 1 initially was an injection well for each of the patterns. KESULTS OF POTENTIOMETKIC MODEL STUDlES Two cases (Cases I and 11) involving equal pressure injections were studied, with the following results. Case Water injection was initiated at Well No. 1; the producing wells (Nos. 2, 3 and 4) were operated at constant and equal bottom-hole pressures. When water broke through at Well No. 2 and achieved the selected water-oil ratio, Well 2 was converted to a water injection well, resulting in two injection and two producing wells. The injection pressures at Wells 1 and 2 were maintained equal and constant; pressures at the producing wells were held equal, but they were lower than those at the injecting wells. A similar process was repeated when water broke through at Well No. 3. The flood was terminated when

By A. S. Odeh

ABSTRACT A simplified model was employed to develop mathematically equations that describe the unsteady-state behavior of naturally fractured reservoirs. The analysis resulted in an equation of flow of radial symmetry whose solution, for the infinite case, is identical in form and function to that describing the unsteady-state behavior of homogeneous reservoirs. Accepting the assumed model, for all practical purposes one cannot distinguish between fractured and homogeneous reservoirs fram pressure build-up and/or drawdown plots. INTRODUCTION The bulk of reservoir engineering research and techniques has been directed toward homogeneous reservoirs, whose physical characteristics, such as porosity and permeability, are considered, on the average, to be constant. However, many prolific reservoirs, especially in the Middle East, are naturally fractured. These reservoirs consist of two distinct elements, namely fractures and matrix, each of which contains its characteristic porosity and permeability. Because of this, the extension of conventional methods of reservoir engineering analysis to fractured reservoirs without mathematical justification could lead to results of uncertain value. The early reported work on artificially and naturally fractured reservoirs consists mainly of papers by Pollard,l Freeman and Natanson,2 and Samara.3 The most familiar method is that of Pollard. A more recent paper by Warren and Root showed how the Pollard method could lead to erroneous results,4 Warren and Root analyzed a plausible two-dimensional model of fractured reservoirs. They concluded that a Horner-type pressure build-up plot of a well producing from a fractured reservoir may be characterized by two parallel linear segments. These segments form the early and the late portions of the build-up plot and are connected by a transitional curve. In our analysis of pressure build-up and drawdown data obtained on several wells from various fractured reservoirs, two parallel straight lines were not observed. In fact, the build-up and drawdown plots were similar in shape to those obtained on homogeneous reservoirs. Fractured reservoirs, due to their complexity, could be represented by various mathematical models, none of which may be completely descriptive and satisfactory for all systems. This is so because the fractures and matrix blocks can be diverse in pattern, size, and geometry not only between one reservoir and another but also within a single reservoir. Therefore, one mathematical model may lead to a satisfactory solution in one case and fail in another. TO understand the behavior of the pressure buildup and drawdown data that were studied, and to explain the shape of the resulting plots, a fractured reservoir model was employed and analyzed mathematically. The model is based on the following assumptions: 1. The matrix blocks act like sources which feed the fractures with fluid; 2. The net fluid movement toward the wellbore obtains only in the fractures; and 3. The fractures' flow capacity and the degree of fracturing of the reservoir are uniform. By the degree of fracturing is meant the fractures' bulk volume per unit reservoir bulk volume. Assumption 3 does not stipulate that either the fractures or the matrix blocks should possess certain size, uniformity, geometric pattern, spacing, or direction. Moreover, this assumption of uniform flow capacity and degree of fracturing should be taken in the same general sense as one accepts uniform permeability and porosity assumptions in a homogeneous reservoir when deriving the unsteady -state fluid flow equation. Thus, the assumption may not be unreasonable, especially if one considers the evidence obtained from examining samples of fractured outcrops and reservoirs. Such samples show that the matrix usually consists of numerous blocks, all of which are small compared to the reservoir dimensions and well spacings. Therefore, the model could be described to represent a "homogeneously" fractured reservoir. la this paper, the fundamental equation of flow

Jan 1, 1966

By T. D. Mueller, H. Dykstra

This paper describes a method for obtaining compositions of gas and oil phases in equilibrium with each other at a given reservoir temperature and pressure as lean or enriched gas is injected into a reservoir oil not in equilibrium with the gas. The method is based on calculation of equilibrium constants, K, from the equation log Kp = A + B F, where p is pressure and F is component characterization factor. A and B are constants that vary with a composition parameter. The paper explains how A and B could be determined with a minimum amount of data. The method consists of calculating equilibrium constants as a function of liquid composition and using the K's to calculate changes in compositiort of injection gas as it successively contacts original resetvoir oil at the gas-oil front and the change in composition of reservoir oil as it is successively contacted by the injection gas in the vicinity of an injection well. An iterative process is required. Two examples of the method are given which show how oil and gas compositions and properties are calculated with the aid of a computer. INTRODUCTION The calculation of recovery from lean-gas or enriched-gas injection into a saturated or under-saturated reservoir oil requires a knowledge of how phase properties change in a reservoir between injection well and producing well. To determine the phase compositions or properties experimentally would be difficult and time consuming, especially if one wanted to look at the effect of various injection gas compositions. For some fields an engineer would want to make preliminary calculations on the economics of gas injection before he makes the decision to spend a corrsiderable sum of money for laboratory work to obtain the necessary fluid properties. A method for calculatine compositions and properties based on a minimum of laboratory data is described. The minimum amount of data required is injection gas and reservoir oil composition and injection gas solubility as a function of pressure for an undersaturated oil, or the compositions of mixtures of reservoir fluid with two or more enriched gases, which mixtures have a bubble-point pressure that is the same as the expected average displacement pressure. On the other hand, if the economics appear to be attractive, more laboratory data can be obtained in the form of equilibrium constants for three or more mixtures of the reservoir fluid and injection gases. The method is based on the calculation of K's from the equation, log Kp = A + B F, where K is equilibrium constant, p is pressure and F is component characterization factor. This method of plotting K data by means of the above equation is described by Hoffman, Crump and Hocott.1 A and B are constants that vary with a composition parameter. It is shown how experimental data are used to determine how A and B vary with composition. BASIS OF METHOD EQUILIBRIUM CONSTANTS Equilibrium constant (K) data are required for this method. The K of each component is obtained from an equation that gives the product of K and pressure as a function of component characterization factor. The characterization factor F = b(l/Tb — l/T), where b is a constant characteristic of a given component, Tb is the boiling point in OR at atmospheric pressure of the given component, and T is the temperature of the system in OR. This method of plotting K data is described by Hoffman, Crump and Hocott.l The straight-line equation of the log Kp - F plot is log hp = log Kop +BFi, where Kop is at F =0, i designates the component, and B is the slope of the line. The factor F can be

Jan 1, 1966

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By E. E. Underwood, L. L. Marsh

Aluminum single crystals, alloyed with 0.042 atomic pet Cu and 0.11 and 1.1 atomic pct Mg, were subjected to constant stress creep tests, tensile tests, and hot hardness measurements within a temperature range of 300° to 866OK. Calculations based on Dorn's temperature-compensated time parameter, 6, gave a value of DH, = 27,000 cal per mol for the activation energy of early creep in aluminum single crystals. Correlations have been obtained for aluminum alloy single crystals with the parameter E for solid solution strengthening, as well as with the parameter F for solid solution hardening, by using a valence of three for aluminum. Limited measurements on tensile specimens show that the slip band density tends to decrease with increasing temperature and with decreasing solute concentration. INCREASING interest is being shown in the mechanisms of plastic deformation in single crystals during tensile and creep testing. The complexity of deformational processes in polycrystalline materials has led to a search for simpler experimental conditions. Numerous creep and tensile investigations have been conducted with pure, metallic single crystals. To a lesser degree, the effects of alloying elements on the tensile properties of single crystals have been determined. However: the literature dealing with the effects of alloying additions in single crystals under creep conditions is vanishingly small. This paper represents an attempt to narrow this gap in the knowledge of the subject. Previous investigations of creep behavior at the Battelle Memorial Institute1-1 have been of great value in the analysis of the present single crystal data. It is equally desirable, however, to ascertain the extent of correspondence between the behavior of single crystal and polycrystalline materials. For this purpose, correlations, similar to those developed for polycrystalline aluminum alloys by Dorn and co-workers, have been made with the single crystal data. The results from this study have tended to confirm and extend those correlations to the case of alloyed single crystals. Materials and Procedures Three dilute binary aluminum alloys were prepared for this investigation from 99.99 + wt pct Al, 99.8 wt pct Mg, and 99.92 wt pct (electrolytic) Cu. The nominal compositions of the alloys were 0.042 atomic pct Cu, and 0.11 and 1.1 atomic pet Mg. Precautions were taken to avoid contamination of the stock during melting and casting of the alloys. After a heat treatment of 8 hr at 925°F the alloys were extruded, then machined into) threaded tensile specimens with a 3 in. reduced section and a 0.505 in. diam. Spectrographic examination showed less than 47 ppm metallic impurities in each alloy. The single crystals were grown by the strain-anneal method, with a critical strain of about 11/4 pet giving the optimum results. In general, 3 in. crystals were obtained with the Al-Cu alloy, but smaller crystals in the magnesium alloys necessitated the use of 2 in. and 1 in. gage lengths with the low and high magnesium alloy specimens, respectively. After an electrolytic polish, the orientation of that portion of the specimen containing the largest single crystal was determined from Laue back-reflection photographs. Tensile tests were conducted at a constant load rate of about 2 lb per min. Creep runs were made in a constant temperature room, under constant stress at the higher creep temperatures, and constant load at the lower temperatures. The eloneation was measured to within ±5 microin. by a specially designed capacitance extensometer. The ex-tensometer arms were attached to the 3 in. specimens at the shoulders of the test piece or, where the crystals were smaller than 3 in., by knife-edge grips.

Jan 1, 1957

By Richard I. Petritz

A brief review of today's processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting' to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967