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By R. W. Hertzberg, R. W. Kraft

A study of the fracture behavior of unidirectwn-ally solidified Cu-Cr eutectic alloy was performed. Fractured whiskers, grain boundaries, and the interface between proeutectic Cr dendrites and the Cu matrix were the predominant failure initiation sites where grain size was larger. Strain induced void formation was restricted at lower solidification rates. This was attributed to a lack of adequate plastic constraint and a probable preferred orientation. A modification of the Crussard et al. model is presented to explain the appearance of "elongated dimples" on the shear fracture surface. A Cu-Cr alloy containing about 1.8 at. pct Cr solidifies by a eutectic reaction forming filamentary crystals of chromium within a continuous copper solid solution matrix.' Webb and Forgeng2 have shown by bend tests that the extracted chromium filaments, which are ordinarily curved and branched (due to random solidification), have the high strengths associated with whiskers. If an ingot of the eutectic alloy is unidirectionally solidified and appropriate control exercised over the thermal gradient, growth rate, and impurity level, the chromium fibers can be forced to solidify as fibers which are substantially parallel to the growth direction, Fig. 1. Uniaxial tensile tests on these straight chromium fibers extracted from controlled ingots3 have confirmed the earlier bend test results on curved fibers. Combining the facts that the strength and modulus of the chromium filaments are higher than the more ductile copper matrix and assuming that a "good bond" exists between the two phases, the Cu-Cr controlled eutectic system fulfills the requirements for effective fiber reinforcement of ductile matrices as established by studies on fiber glass reinforced plastics and other two-phase systems.4 Therefore, it was decided to study the fracture characteristics of morphologically simple specimens of chromium fiber reinforced copper (i.e., specimens of the controlled eutectic with substantially parallel reinforcing fibers) with the objective of establishing the dominant aspects of fracture. PREVIOUS WORK Comparatively little work has been done to understand the manner in which ductile alloys fail be- cause of the limited demand for this kind of information. Ordinarily ductility is specified for safety or similar reasons and when a part deforms plastically its useful life is terminated. In recent years, however, a number of investigators have begun to

Jan 1, 1963

By John L. Miles

John L. Miles (Arthur D. Little, 1nc.)—Pollack and orris" have reported measurements on electron tunneling through A1-A12O3-A1 sandwiches in which the oxide was formed by gaseous oxidation in a glow discharge. From these measurements they deduced the asymmetry of the barrier and, since this is small, conclude that the mechanism suggested by Mott19 for the growth of oxide in thin A12O3 films is inapplicable. In earlier papers20 Pollack and Morris report similar work for oxide films grown thermally. In this case they find a greater asymmetry and conclude that the Mott mechanism is valid. I would like to point out that both these conclusions are quite unjustified. Mott suggests that the growth of the oxide film on aluminum results from the passage of ions through the already present film of oxide under the action of an electric field. This field results from a constant voltage which is in effect a contact potential between metal on one side of the barrier and adsorbed oxygen ions on the other side of the barrier. The theory does not require that the oxide grown is nonuniform either in stoichiometry or structure. It does however specifically assume that the partial layer of ionized oxygen on the surface remains adsorbed on the surface of the growing oxide. In other words, the so-called "built-in field" remains in the oxide only as long as the ionized oxygen is present. When a counter electrode of aluminum is deposited on the oxide, it will react with the adsorbed oxygen on the surface of the oxide, thus forming a small additional amount of oxide. It is clear, then, that there is no requirement in the Mott theory of oxide growth which would necessitate tunneling currents through an Al-A1203-A1 sample to be different when the polarity is reversed. Neither does the theory eliminate the possibility that some additional mechanism could cause the tunneling barrier to be asymmetric and hence tunneling currents to be a function of polarity in such a sandwich. Thus these tunneling-currents measurements are not germane to the question of whether the Mott mechanism is the true method of growth of aluminum oxide films. In fact, it is not surprising that there should be a difference between the oxide properties at the two interfaces (with resulting asymmetry in the tunneling barrier) since the growth conditions and growth rates must have been quite different at these two positions. S. R. Pollack and C. E. Morris (authors' reply)— The point raised by Miles above is one has caused some confusion in the past. The following is an attempt to clarify this point. The built-in field which is responsible for the growth of the thermal oxide at low temperatures arises, according to Mott, because of the passage of electrons from the Fermi surface of the oxidizing metal to surface states introduced by the adsorbed oxygen. It is assumed that the energy of these surface states lies below the Fermi energy of the metal. Electrons therefore continue to flow from the metal to the surface until the built-in electric field raises the potential energy of the surface states to the value of the Fermi energy in the metal, at which time equilibrium is obtained between the surface states and the metal. That is in equilibrium as many excess electrons pass from the metal to the surface per unit time as vice versa. The surface of the oxide prior to deposition of a metallic counterelectrode can then be pictured as follows. The Fermi energy lies in the energy gap of the oxide and is essentially pinned at the energy of the oxygen surface states. The vacuum work function of the oxide is then given by the sum of the electron affinity of the oxide (i.e., the difference in energy between the vacuum and the conduction-band minimum) plus the energy difference between the conduction-band minimum and the Fermi energy. The deposition of a metal onto the surface of the oxide can result in a transfer of electrons across the extremely thin oxide only if there is a contact potential difference between the deposited metal and the parent metal or oxide. That is if the vacuum work function of the deposited metal differs from that of the parent metal, then charge can be redistributed across the oxide in order to equilibriate the Fermi energy across the structure. (It should be

Jan 1, 1965

By E. D. McMurry

INTRODUCTION Before discussing the use of the free piston; it may be well to explain briefly the type of gas lift valves with which the loo] is designed to function. The gas lift valve ii nothing more or less than a small back pressure regulator. It; construction consists of an outer hous ing covering a seamless metallic bellows in such a way as in form a sealed pressure vessel or pressure dome. To the bellow* in attached a stem and to this stem is attached a .rating member. When the valve is run into the hole, a pre-delermined pressure charge is placed in the pressure dome. As shown in Fig. 1. the valve is furnished in four different major assem-blies. to accomplish good results in different types of wells. The valve is mounted on a pup joint (Fig. 2a) : the eoin-plele assembly is entered into the tubing siring at the desired location. Each valve is furnished with a revere flow check valve (Fig. 2-b) to eliminate any back wash through the mechanism. Valve action is as follows: At any time the casing pressure is allowed to exceed the pressure forces within the pressure dome of the valve, the valve simply opens and passes gas from the rasing annulus into the tubing. When the casing pressure forces arc allowed to bleed to a force less than the pressure force within the dome, of the valve. the valve closes. With this type of construction. it is possible to open and close the valve or valves at will from the surface, the medium of the gas pressure in the rasing annnlus. The cycle of operation is governed by a tine cycle motor valve, commonly referred to as a gas lift interutitter or gas life surfacr controller (Fig. 3). In actual practice. after the well is unloaded only one valve is in operation . . . all other valve.: remain in the closed position. On pre-determined time cycles, it is possible to open and close this operating valve at will, and to pass the desired amount of gas through this valve wheneler needed. This method of gas lift is widelv used and has been found In be very efficient. However, it has long been known that even greater efficiency would be obtained if it were possible to place Piston between the injected gas and the fluid head. The free piston which will be discussed here was designed to accomplish this end and has been found to do so with very satisfactory results. DESIGN AND OPERATION OF THE FREE PISTON Basically. the free piston consist- of a telescoping assembly in which are incorporated the various control and operating parts (Fig. A set of sleeve valves which are opened and closed by movement of the telescoping section is contained in the. tool. A cross section of the free piston is shown in Fig. 4-11, 'rile main body cotain- a seamless monel bellows of the same type as that generally used in pressure charged gas lift valves (Fig. 4-c), and a valve core to permit placing a pressure charge in the bellows before the free piston is placed in service. The bellows is the main control unit of the free piston and performs two function: 1. It governs the opening and closing of the sleeve valves. a.: dictated by the producing activities of the well in which the piston is operating. 2. In its normal position, it holds a rubber packer in an elongated position to permit passage of fluid between the packer and the tubing walls. The lower section of the free piston contains a hydraulic shock absorber which cushions the return of the tool to its

Jan 1, 1953

By U. N. Bhrany, J. H. Brown

The specifications of particle size and the size analyses of fine particulate materials are commonly presented without reference to the method of analysis. A review of the various sizing methods showed that not only numerous sources of error but also different definitions of size are inherent in the different methods of analysis. To demonstrate the magnitude of the differences, the size distribution of finely crushed quartz was determined by several methods and a critical comparison of the data was made. The experimental results show that appreciably different sizes may be indicated for one material depending on the method of analysis used. However, because the shape of the size-distribution curves determined by almost all methods was constant, a simple method of correlating the data can be adopted. Conversion factors, by which size measurements obtained by the various methods can be expressed in terms of screen sizes, are presented as one method of correlating the results. The size analysis and size specification for lump rock and particulate materials are commonly determined with sieves. With this technique, a readily reproducible measure of size can be obtained merely by duplicating the sieve and the method of sizing. For coarse materials, such as lumps of rock, this technique is simple and effective; and the effects of properties of the material such as shape can be readily understood. When very small particles are measured, however, problems arise. Small sieves are difficult to construct and maintain, and size separations become sensitive to the analytical procedure. For these difficult sieve sizes and for still smaller particles, other sizing techniques employing, for example, sedimentation, light extinction, and microscopy are available. Because these various techniques employ different size-dependent responses to establish size, it is appropriate to examine them and the results they yield to determine their relationships and their limitations. The 'size' of a lump of rock is not an absolute quantity, but rather a defined one. With sieves, for example, the size is defined by the screen aperture and no reference is made to the actual shape of the particle, yet only in the case of a regular body, such as a sphere, can the sieve size be related to the shape. With sieves only two dimensions of a particle can be suggested, for the sieve makes no allowance for the length of the particle passing through an aperture. Similarly, the size of a particle as measured by a microscopic technique need bear no relationship to the size as measured by sieves, although the two measurements may be related statistically. In fact, all size measurements are not only defined quantities, but the measurement actually used is an average that is controlled by the technique employed and, hopefully, reflects the property in question of the material of interest. Many papers have been presented that illustrate the accuracy of the various sizing methods, present the advantages of certain methods for certain applications, and describe the principles and technical backgrounds of the various methods. No attempt will be made in the present paper to review this work in detail. The purpose of the present paper is to examine the limitations of the various sizing methods, and to demonstrate experimentally the relationships between the sizes as determined by the various methods of analysis. It is hoped that by recognition of these limitations and relationships, errors in size specification and size interpretation will be avoided. REVIEW OF SIZING METHODS In specifying the size of a material, not only the data but also the method of measurement must be stated. For example, the size of the lump might be specified as its total volume, as its weight, as its maximum dimension, or as its minimum cross section; any one definition might be completely satisfactory for one problem, but not for another. In practice, size analyses follow four basic approaches and fortunately, the conditions that restrict each approach are known. These major methods include: 1) screen analysis, 2) direct measurement of particle dimensions, 3) determination of equivalent spherical size in response to fluid flow, and 4) specific surface determination. Each of these techniques has several variations and some new techniques are also available, but the limitations of the basic techniques are sufficient to permit at least a preliminary

Jan 1, 1962

By Peretti, E. A.

Since its development about forty years ago by J. V. N. Dorr (Cyanidation and Concentration of Gold and Silver Ores, McGraw Hill Book Co., 1936, 1-5), and others, continuous countercurrent decantation has not only become one of the standard methods for extracting gold and silver from their ores, but has also found wide application in other metallurgical and chemical industries. In 1917 L. B. Eames published an excellent paper (Countercurrent Decantation, Trans AIME, 1917, 57, 143- 158), in which he determined the effects of grade of ore, ratio of solution precipitated to ore treated, variations in the density of the thickener spigot discharge and variations in the value of the barren solution upon the gold assay of the solutions discharged from the thickeners in the system. Eames showed that, other things being equal, the dissolved gold lost in the tailing varies directly as the value of the ore and as the value of the barren solution. The tailing loss de- creases rapidly as the ratio of solution precipitated to ore treated is increased to about three or four to one. Beyond this point the improvement is negligible.

Jan 1, 1949

By J. B. Stubbins, R. A. Blais

Extensive geological work was initiated — and continues — when operations of the Iron Ore Co. of Canada commenced in the Labrador-New Quebec area. Such geological operations include: mapping, test pitting, drilling, underground workings, volume factor and structure tests, and the calculation of ore grades and tonnages. Details of such work are given. Development is carried sufficiently ahead of mining to provide reliable tonnage and grade estimates and allow final mine planning. In order to make full use of geology in mining operations, the pit engineer combines the duties of geologist and mining engineer. The iron deposits of the Knob Lake range are located in the central part of the Labrador peninsula, a territory nearly twice the size of Texas, which is bounded by Hudson Bay on the west, Hudson Strait on the north, the Atlantic Ocean on the east and the Gulf of St. Lawrence on the south. The mining district proper is about 1000 miles northeast of Toronto. A 360-mile railroad links this mining area to the port of Sept-Iles on the Gulf of St. Lawrence. Schef-ferville, which is only a few miles from the open-pit mines, is the center of operations of the Iron Ore Co. of Canada. It has a population of nearly 5000. The nearest settlement is Labrador City, some 120 miles to the south, where this company is erecting a large plant for beneficiating its huge reserves of local low-grade iron ores. HISTORY The mineral possibilities of the area were recognized as early as the end of the last century, when A.P. LOW' of the Geological Survey of Canada made his famous trek across the Labrador Peninsula. After mapping several belts of iron formation, Lovr recommended that the area be thoroughly prospected for iron. In 1929, two well known Canadian geologists, J.E. Gill and U'.F. James, led a private expedition in central Labrador and discovered the first deposit of high-grade iron ore near what is now the Ruth Lake Mine. In 1936 the Labrador Mining and Exploration Co. was formed to 11ake over a prospecting concession of over 20,000 sq miles in central Labrador. An adjoining concession of 3900 sq miles in New Quebec was obtained in 1942 by Hollinger Consolidated Gold Mines, which had just Purchased the Labrador Co. The same year the M.A. Hanna Co. Purchased an interest in both exploration companies. From 1942 to 1950 extensive exploration was conducted by the Hollinger-Hanna technical staff to systematically appraise these vast concessions. More than 40 deposits of high grade ore were found and, by the end of 1950, the total ore reserves reached 418 million tons. In 1949 five American steel companies joined the Hollinger-Hanna interests and formed the Iron Ore Co. of Canada. Financing and full-scale construction were decided upon in 1950. This included the construction of a 360-mile railroad through very difficult terrain, the erection of two hydroelectric plants, the installation of terminal port facilities at Sept-IIes, the building of a modern town-site at Schefferville, the construction of crushing and screening plants, and the preparation of deposits for mining. Ore was first shipped in July 1954. Total open-pit mine production to date is 66 million long tons of direct-shipping ore. GEOLOGICAL ENGINEERING The above achievements would not have been possible without irtegrated teamwork of people of diverse skills and extensive use of geology. In their paper on the role of geologists in the development of this iron ore field, (Gustafson and Moss1 rightly emphasized the difficulties facing the early workers in the area. In an uninhabited land with no roads or railroads and no navigable rivers leading to the interior, everything had to be flown in. It was not until 1948 that aerial photographs and adequate base maps became available. In spite of these and other difficulties, an impressive amount of field work has been done since 1942. Nearly all this work has been directed by geological engineers and geologists. About 15,000 :sq miles have been geologically

Jan 1, 1962

By J. E. Powell, F. H. Spedding

WHILE rare earths are reported to be widely distributed in nature and are not really rare," in practice, there are only a few minerals which are sufficiently rich in rare earths to serve as practical sources. Perhaps the best known of these is monazite which is a phosphate mineral containing rare earths and thorium. This mineral occurs as a dense brown sand in gravel beds and is particularly rich in the light rare earths of the cerium subgroup. This mineral is processed commercially for its thorium, cerium, and lanthanum content, and, consequently, furnishes rich concentrates from which neodymium, praseodymium, samarium, europium, and gadolinium may be obtained. Unfortunately, monazite is rather lean in rare earths heavier than gadolinium. A second mineral which is rich in the light rare earths is bastnasite, a fluoro-carbonate. Extensive deposits of this ore have been discovered in the western United States and have received considerable newspaper publicity in recent years. While bastnasite is very rich with respect to cerium, lanthanum, and neodymium, it contains even less heavy rare earths than does monazite. One of the better sources of heavy rare earths of the yttrium subgroup is gadolinite, a black silicate rock from which the rare-earth content can be extracted readily by acid leaching. It is obtained chiefly from Norway at the present time, although there are known deposits in the United States. Other sources of heavy rare earths include fergu-sonite, euxenite, and samarskite which are refractory tantalo-columbate ores. These minerals require caustic fusion or reduction to carbides with carbon before the rare-earth content can be extracted. All of the minerals which are rich in the heavy rare earths contain yttrium as a major constituent. After the rare earths have been extracted as a group from an ore by chemical means, it is generally convenient to precipitate them from acid media with oxalic acid in order to eliminate certain non-rare-earth impurities such as iron, beryllium, etc., which are usually present. The oxalate can then be readily ignited to R2O3. The oxide can be dissolved in acid and is the starting point for subsequent separation into the pure components. Perhaps the principal reason why the rare earths have not been studied as extensively as other elements of the periodic table, whose natural abundances are comparable, is that they are extremely difficult to separate from each other by the usual chemical means. Prior to 1945, the separation of one trivalent rare earth from another was a laborious process. All separations were based on repeated fractionation processes, i.e., fractional precipitation, fractional decomposition, fractional crystallization, etc. These processes were repeated from a few hundred to many thousands of times in order to obtain individual rare-earth salts of reasonable purity. Of course, mention should be made that, in the few cases where a rare earth could be oxidized or reduced to a valence state other than three, more conventional chemical means could be utilized to separate the oxidized or reduced ion from the other normally trivalent rare earths. The ionic states which deserve special mention are CeIV, SmII, Eu11, and Yb11. When it is possible to remove an element of the series efficiently, due to an optional valence state, its immediate neighbors also become easier to isolate. For example, binary mixtures of lanthanum and cerium, and praseodymium and cerium can be obtained by a relatively small number of fractional operations. The tetravalent state of cerium then allows the complete resolution of the binary mixtures by ordinary chemical means. Although the tetravalent state of cerium has been known for a long time, the divalent states of samarium, europium, and ytterbium were not used extensively in separations prior to 1930 because they are relatively unstable in aqueous media.'-" No attempt will be made to give a comprehensive review of the extensive literature dealing with the separation of rare earths. Rather, this paper will be confined to a review of those methods which have been developed at Iowa State College during recent years, and which have proved extraordinarily successful for the isolation of highly pure rare earths in quantity. It was obvious that, if pure rare earths were to become generally available, methods would have to be developed wherein the thousands of fractional operations made necessary by the similarity of rare-earth properties could be performed automatically. The development of chromatographic techniques and ion-exchange resins appeared to offer a mechanism by which this objective could be accomplished. A number of early attempts were made to separate rare earths by these means; for example, Russell and Pearce12 passed a mixture of rare earths through a cation-exchange column and reported

Jan 1, 1955

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown's paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).' Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By W. E. Bearce

The recent concern for the recovery of even the finest fractions of coal preparation plant feeds has created needs for new equipment. Thermal dryers currently available have difficulty reducing the filter cake moisture on down to the desired point. This difficulty involves 1) the physical problem of handling this wet, sticky material and making each particle accessible to the hot gases, and 2) removing the extremely fine dried particles from the cooled gases. The dryer described in this paper handles the first of these problems, and eliminates the second by the substitution of steel balls for air as the heat transfer medium. As a general statement, the cost of preparing coal for market is inversely proportional to the size of the lumps or particles. In the not too distant past the finer sizes were discarded as being uneconomical to treat and this practice might be still continuing if it were not for the insistence of the public that this material be kept out of our streams. This being the only cost-free outlet, the disposal of fine refuse became a significant item of expense in every preparation plant. When this happened it was only reasonable to look to the recovery of the values in this material, not only to defray this expense, but to reduce the tonnage which had to be wasted. There seemed to be no device available suited to reducing the moisture in this material to what the market requires. All of the fine coal dryers commonly employed make use of air to bring the heat of combustion into contact with the coal particles. Any device employing air as a heat transfer medium, has the following two strikes against it in attempting to handle 28 mesh by 0 filter cake: 1) It is practically impossible to bring the hot air into intimate contact with the enormous number of fine particles stuck together in the cake. 2) Even if this can be effected, it is impossible to remove the dried coal from the air. A wet scrubber must be employed, the discharge of which must go back to the filter and dryer as a circulating load of the most objectionable sort, being the extreme fines. Various compromises have been used to cope with the problem of drying this relatively small tonnage of high moisture coal. Often some of the dried coal is mixed back with the feed to the dryer in an attempt to make the mixture more handleable and more available to contact with the hot air than the filter cake alone would be. This may help to some extent with the first problem but it does nothing about the second and a dryer operated in this way has to be oversized. Sometimes the filter cake is mixed with a coarser fraction for the same reason. Here again, while this may make a mixture (the particles of which are more readily brought into contact with the hot air), the problem of getting the fine coal out of the air remains and a larger percentage of the total coal to be dried is handled by the most expensive means. Mechanical dewatering has accounted for more and more of total coal drying lately and in many cases would satisfactorily handle the whole load, down to 28 mesh, if there were a means available for doing a good job on the —28 mesh by itself. The dryer which is the subject of this paper was designed expressly for doing this job — drying fine material by itself regardless of how wet it may be to start with, how fine it may be, or how gummy and sticky these properties in combination may make it. The essential features are depicted in Fig. 1. A rotating cylinder is supported on a frame in such a way that one end may be raised or lowered by hy-

Jan 1, 1968

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By J. B. Mudd

Introduction It is difficult to think of any activity on which mankind has been more dependent than mining, and certainly there is much evidence in almost every part of the world of old workings that clearly demonstrate that man from earliest times has dug and toiled to take from the earth precious stones, metals and materials that from time to time have been essential or of value to him. In step with social development and industrial and technological advances the tempo of mining activity, regulated only by the laws of supply and demand, has quickened and in this century has accelerated rapidly in keeping with its dramatic development. Indeed, the rate of change of events has been such that if it were to continue to accelerate as fast as it has over the past decade there is reason to wonder how the insatiable demands for metals and minerals are to be met in the years that lie ahead. Shallow mines containing high-grade ore deposits either have been or are being rapidly mined out and their place can only be taken in general by ore lying at greater depth, or by ore of low grade, situated for the most part in remote and in underdeveloped areas. The cost of exploration and development is rising at an alarming rate, with the result that the expenditure now required to bring a mine to production far exceeds anything previously contemplated. It is estimated that the total capital required to maintain existing operations and develop new ones during the next 5 years will be of the order of $50,000 million and of this, new capital to bring new mines to production will be of the order of $3,000 million. Today no single mining finance company can, from its own resources, find all the money for a major mining development, and as a consequence there has been a strong trend toward joint ventures and to the formation of multinational consortiums. International lending institutions already play an important part in financing many new mining projects and their participation provides the financial umbrella under which other lenders can invest with greater security. There is little doubt that to finance the costly ventures in the future, governments and international lending agencies, banks and finance

Jan 1, 1971

By R. E. Smallman, I. Milne

The deformation behavior of single crystals of Nb-Mo alloys has been investigated with particular reference to the influence of composition, orientation, and temperature. Strong solid-solution hardening was observed reaching a maximum at the equiatomic cotrlposition and can be attributed to the difference in atomic size between niobium and molybdenutrz. Changes in the form of stress-strain curve, as shown by a high work-hardening rate and restricted elongation to fracture, were observed at a composition of Nb-85 pct Mo and are attributed to the presence of MozC DreciDitate. Conjugate slip was only extensive in dilute alloy samples; at the 50/50 composition deformation rnainly occurred by primary slip, and the onset of conjugate slip gave rise to failure by cleavage on (100). The variation of yield stress of Nb-50 pet Mo with orientation was consistent with slip on (011)(111) slip systems. The temperature deperndence of the yield stress between -196" and 250°C was similar to that of pure bcc metals, but at a much higher stress level; no evidence for twinning %as found. IN recent years the deformation behavior of various pure metals in groups VA and VIA has received considerable attention, but surprisingly little work has been carried out on binary alloys made by mixing metals from the two groups. Such an investigation would be of interest since single crystals of metals of group VA have been shown to deform characteristically with a multistage deformation curve1"3 while a parabolic type of deformation curve has been reported for most of the group VIA metals.4'5 It has been suggested by Law ley and Gaigher~ that the difficulty encountered in obtaining multistage deformation curves for molybdenum in group VIA was possibly because of the presence of a microprecipitate of MozC which they observed even at carbon contents as low as 11 ppm. Recently a multistage deformation curve has been reported for molybdenum ," although the stages are not so definitive as those for group VA metals. The binary alloys of the particular refractory metals which have been investigated in single-crystal form include Ta-w,' Ta- Mo,' and Nb- Na." While a large amount of hardening was observed for alloys of the Ta-W and Ta-Mo systems, associated with room-temperature brittleness for alloys approaching the equiatomic composition, Ta-Nb remained ductile over the complete composition range with little or no solution hardening. Other systems have been investigated by hardness measurements on polycrystalline material and a discussion of the hardening of these alloys has been presented by ~udman." The purpose of the present investigation was to examine the deformation behavior of Nb-Mo alloys in detail, with particular reference to alloy composition and single-crystal orientation. In this way it was hoped to shed some light upon the restricted ductility of these alloy specimens. 1) EXPERIMENTAL PROCEDURE The starting materials were obtained in the form of beam-melted niobium rod and sintered molybdenum rod of suitable dimensions. Since niobium and molybdenum form a complete solid-solution series at all temperatures, alloy single crystals were produced by melting the two constituents together in an electron bombardment furnace (EBM). To produce specimens free from segregation a molten zone was passed over the length of each rod six times in alternate directions at a speed of 10 in. per hr. Typical specimens were analyzed for interstitial impurities by gas analysis and for metallic impurities by spectrographic analysis. The results of this analysis are shown in Table I. Many of the tensile specimens were also analyzed (after testing) by scanning the gage length in an electron beam microanalyzer, from which it was found possible to predict the approximate composition of a specimen from the original proportions of each element in the EBM. The tensile specimens were made with a gage length of 0.5 in. and diameter of 0.075 in., using a Servomet Spark machine. By careful machining on the finest range for the final i hr of this technique, surface cracks could be reduced to the level where they were easily removed by electropolishing in a solution of nitric and hydrofluoric acids. The specimens were strained at a rate of 10 4 sec-' using friction grips designed to prevent accidental straining and maintain a good alignment before straining. The orientations of the individual specimens tested are shown in Fig. 1 and the corresponding compositions listed in Table I1 together with collated experimental data. 2)RESULTS a) General Deformation Behavior. The effect of composition on the room-temperature deformation curves of similarly oriented specimens is shown in Fig. 2. The yield stresses of the pure constituents, while not the lowest reported to date, were at least comparable with existing data. Although the solution hardening was large for alloys at either end of the phase diagram, and comparable with the Ta-W solution-hardening data of Ferris et a1.,8 the low work-hardening rate characteristic of niobium was sustained until a composition of Nb-85 pct MO had been reached. Associated with the peak yield stress ob-

Jan 1, 1969

By R. V. Smith

The theoretical background for calculating friction factors for flow in gas wells by two methods is presented. The first method, requiring pressures, temperatures and specific volumes of the flowing fluids at various depths in the well bore, shows how the mechanical-energy-balance equation for vertical flow may be graphically integrated over the actual path of the expansion of the fluid in the well. Thus, assumptions regarding the effective temperature and effective compressibility of the fluid in the well are avoided. The second method presents an equation derived on a basis of the assumptions that both the temperature and the compressibility are fixed at constant effective values throughout the flowing column of gas. The second method provides a convenient and practical means of calculating friction factors for gas wells and lends itself readily to the problem of calculating subsurface pressures in a flowing gas well. The application of both methods to actual test data taken on a flowing gas well is illustrated in the paper. INTRODUCTION As friction factors for the producing strings of flowing gas wells cannot be measured directly and must be calculated from flow-test data, study of the methods of arriving at friction factors is a necessary adjunct to understanding the characteristics of flow in gas wells. There are two methods of calculating friction factors for gas wells; they differ from one another mainly in the treatment of the path of expansion of the fluid in the well. In the flowing well, the energy consumed in lifting the fluid from the bottom to the top of the well, overcoming the friction between the moving fluid and the pipe walls, and increasing the velocity of the fluid as it flows up the producing string is supplied by expansion of the flowing fluid. The available energy is determined by the expansion of the fluid that follows a path determined by conditions of temperature, compressibility and phase changes of the fluid during the expansion. A means of evaluating the available energy in a flowing gas well and determining the proportion of the available energy used in lifting the gas, overcoming friction, and increasing the velocity of flow is developed in this report. Knowing how much energy is consumed in overcoming friction makes it possible to calculate friction factors for given flow rates in given sizes of pipes in wells. Friction coefficients, as used in this report, are dimension- less proportionality multipliers used in the flow equations to satisfy the equality between the terms of the equation. The square root of the reciprocal of the friction coefficient is termed the friction factor. It has been known for many years that friction factors may be computed directly from mathematical formulas based on certain assumptions regarding the temperature and compressibility of the moving fluid in a well. A general equation is presented in this report without assumptions for vertical flow of fluids and a conventional-type equation is derived on the basis of assumptions that fix the temperature and compressibility at constant values. Accurate pressures at the sand faces in wells are required in the method of determining the productivity of gas wells, as outlined by Rawlins and Schellhardt1 in Bureau of Mines Monograph 7. Where measurements are not made with subsurface-pressure gauge; or static gas columns are unavailable, flowing pressures customarily are calculated at the sand face in the well by the use of the well-known Weymouth formula1. Natural gas engineers have realized that errors introduced by the use of friction factors as given by the Weymouth formula are relatively unimportant in testing low-capacity gas wells; they also know that such factors are important considerations in testing large-capacity gas wells. Accordingly. present research on the productivity of gas wells at the Petroleum Experiment Station of the Bureau of Mines, Bartlesville, Okla., is being directed toward measurement of the pressure loss due to friction in flowing gas wells. It is beyond the scope of this report to show how friction factors vary with rate of flow and in pipes of different diameters, as it is intended only to develop and illustrate the use of mathematical expressions for calculating friction factors from flow-test data. The equations presented apply only to turbulent flow in circular pipes. ENERGY RELATIONS FOR FLOW OF FLUIDS2 The concept of conservation of energy is usually the basis of any study of fluid flow through vertical pipes as in gas wells, horizontal pipe lines, or orifices. In deriving equations, the following symbols are used:

Jan 1, 1950

By AIME AIME

T HE year 1920 will be a memorable one in the history of the world's coal supply. The prices reached were the highest of modern times, and as usually happens at such a time, the quality of the output deteriorated. In the last two years of the war, the world's output had risen close to the pre-war level. After the armistice, however, the cessation of munitions manufacture and the delay in resumption of normal business curtailed the demand for coal. Industrial disputes both in Europe and America closed many mines late in 1919 and further reduced the supply. Thus when in 1920 the world set its face to work again and industrial activity was resumed where resumption was possible, consumers' reserves of fuel proved insufficient and an almost universal feeling of apprehension over the coal supply swept around the world. The reasons for this alarm-lately a thing of the past-become clear when the world's production in 1920 is cast up.

Jan 1, 1921

By R. A. Morse, W. O. Keller

The properties of limestone reservoir rocks such as the distribution and degree of continuity of the pore systems, and the relative volumes and permeabilities of the systems making up the complex cause large variations between performance of individual limestone reservoirs and their susceptibility to secondary recovery methods. The effects of these factors on the mechanism of fluid flow cannot be adequately evaluated with presently developed concepts, laboratory data, and geological information. The observance and interpretation of the performance of individual limestone reservoirs provides, at present, the most adequate approach for evaluating the integrated effects upon performance of the many. now immeasurable variations in the properties of limestone reservoirs. INTRODUCTION The development and application of techniques for increasing the efficiency of oil recovery from natural reservoirs is a problem of primary importance to the industry. During the past several years, a great deal of effort has been expended by the technical personnel of the industry toward the improvement of present known methods of oil recovery. and evaluating the factors which control the susceptibility of particular reservoir types to economic application of secondary recovery methods. Providing adequate and accurate laboratory data on the properties of the reservoir rock and its contained fluids. together with good production statistics, are available, methods have been evolved for estimating with reasonable accuracy the performance of an oil reservoir under either continued natural depletion or conditions imposed by introducing additional displacing fluid into the reservoir from an extraneous source through the injection of gas and/or water. The susceptibility of limestone reservoirs to secondary recovery by gas injection is very much dependent upon gas-oil relative permeability relationships for the reservoir in question. In a rock formation in which the porosity is of the intergranular type such as is found in sand stones and some non-fractured dolomites, a representative sample of the pore structure can be obtained in a small core plug. In this type of reservoir, it has been shown that relative permeability data obtained from laboratory experiments can be Properly applied to evaluate the flow relationships actually observed during the depletion of a reservoir. In addition, a good idea of the fraction of the reservoir which will be swept by the injected gas may be obtained from the spacing pattern used and the permeability profile of cored wells. From these data, it has been demonstrated that reliable estimates of performance and recoveries under gas injection operations can be made for reservoirs in which the Porosity is of the intergranular type. Limestone reservoirs on the other hand often present much more complex problems. One reason that the performance of limestone reservoirs is so variable is that there may be, in reality. two or more pore systems, the integrated performance of which will depend upon the physical properties of each system and their inter-relationship. For instance, in a limestone reservoir, the main pore structure, as far as void spaces for storage of hydrocarbons is concerned, may be represented by the intergranular openings of the rock. Usually in limes and dolomites, the intergranular pore openings are very small and the matrix permeabilities extremely low. Often, as in the case of Many dolomite and oolitic lime reservoirs, this is the only pore system, and performance is observed to be very similar to that of a sand stone of similar permeability. However, in the great majority of' the limestone reservoirs, there is present, in addition to the intergranular pore system, a complementary system of openings caused by fracturing or solution.',' The openings in the latter system are usually many times more permeable than the intergranular pore system due to their much larger size, and may contribute almost all the fluid carrying capacity of the formation, even though their volume may be a very small part of the total pore space in the reservoir. Obviously, the performance of such a complex under either primary or secondary control will deend upon the distribution and degree of continuity of both systems, the relative volumes and permeabilities of the

Jan 1, 1949

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation's model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,' which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson' showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation's model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic' displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. 'To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard's Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By R. A. Morse, W. O. Keller

The properties of limestone reservoir rocks such as the distribution and degree of continuity of the pore systems, and the relative volumes and permeabilities of the systems making up the complex cause large variations between performance of individual limestone reservoirs and their susceptibility to secondary recovery methods. The effects of these factors on the mechanism of fluid flow cannot be adequately evaluated with presently developed concepts, laboratory data, and geological information. The observance and interpretation of the performance of individual limestone reservoirs provides, at present, the most adequate approach for evaluating the integrated effects upon performance of the many. now immeasurable variations in the properties of limestone reservoirs. INTRODUCTION The development and application of techniques for increasing the efficiency of oil recovery from natural reservoirs is a problem of primary importance to the industry. During the past several years, a great deal of effort has been expended by the technical personnel of the industry toward the improvement of present known methods of oil recovery. and evaluating the factors which control the susceptibility of particular reservoir types to economic application of secondary recovery methods. Providing adequate and accurate laboratory data on the properties of the reservoir rock and its contained fluids. together with good production statistics, are available, methods have been evolved for estimating with reasonable accuracy the performance of an oil reservoir under either continued natural depletion or conditions imposed by introducing additional displacing fluid into the reservoir from an extraneous source through the injection of gas and/or water. The susceptibility of limestone reservoirs to secondary recovery by gas injection is very much dependent upon gas-oil relative permeability relationships for the reservoir in question. In a rock formation in which the porosity is of the intergranular type such as is found in sand stones and some non-fractured dolomites, a representative sample of the pore structure can be obtained in a small core plug. In this type of reservoir, it has been shown that relative permeability data obtained from laboratory experiments can be Properly applied to evaluate the flow relationships actually observed during the depletion of a reservoir. In addition, a good idea of the fraction of the reservoir which will be swept by the injected gas may be obtained from the spacing pattern used and the permeability profile of cored wells. From these data, it has been demonstrated that reliable estimates of performance and recoveries under gas injection operations can be made for reservoirs in which the Porosity is of the intergranular type. Limestone reservoirs on the other hand often present much more complex problems. One reason that the performance of limestone reservoirs is so variable is that there may be, in reality. two or more pore systems, the integrated performance of which will depend upon the physical properties of each system and their inter-relationship. For instance, in a limestone reservoir, the main pore structure, as far as void spaces for storage of hydrocarbons is concerned, may be represented by the intergranular openings of the rock. Usually in limes and dolomites, the intergranular pore openings are very small and the matrix permeabilities extremely low. Often, as in the case of Many dolomite and oolitic lime reservoirs, this is the only pore system, and performance is observed to be very similar to that of a sand stone of similar permeability. However, in the great majority of' the limestone reservoirs, there is present, in addition to the intergranular pore system, a complementary system of openings caused by fracturing or solution.',' The openings in the latter system are usually many times more permeable than the intergranular pore system due to their much larger size, and may contribute almost all the fluid carrying capacity of the formation, even though their volume may be a very small part of the total pore space in the reservoir. Obviously, the performance of such a complex under either primary or secondary control will deend upon the distribution and degree of continuity of both systems, the relative volumes and permeabilities of the

Jan 1, 1949