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By Gerald Sherman

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

Jan 1, 1951

By G. W. Thomas

A simplified mathematical model of underground conduction heating in a system of limited permeability is presented. The model applies to underground retorting of oil shale, or to reservoirs containing extremely heavy oils. We assume that heat is introduced at a constant rate into a horizontal fracture which communicates between wells. The radial temperature distribution along the fractured surface is approximated by a step-function. Heat transfer away from the fracture is assumed to be by vertical conduction, and all convection effects are neglected. The model also takes into account the possible temperature dependence of thermal conductivity. A general expression for calculating the growth of the step-function temperature distribution with time is derived. The use of this expression and solutions to the one-dimensional heat equation make it possible to construct isotherms. Expressions for calculating .oil recovery, well spacing and heat efficiency are also given. An example calculation is presented for the conduction heating process in oil shale. Finally, the effect of the heat transfer coefficient between the gas and the fracture boundaries is investigated. INTRODUCTION Thermal recovery processes of oil recovery fall into the four general areas of hot fluid injection, forward combustion, reverse combustion and conduction heating. The first three of* these processes have been rather extensively studied in the past decade from both the experimental and theoretical points of view. As a result, it is possible to make reasonable engineering predictions and analyses of these processes. Little attention has been devoted, however, to the conduction heating process other than to note its possible utility.I To a certain extent, conduction heating cannot be divorced from the other regimes cited above, insofar as these provide the source of heat energy. In the conduction heating process, heat is introduced (either by combustion in the forward or reverse mode or by hot fluid injection) into a small fraction of the total reservoir thickness. This fraction may be either a streak of high permeability or an interwell fracture. Heat penetrates by conduction into the adjacent, less permeable regions of the oil-bearing rock, where the direction of conduction is essentially perpendicular to the streak or fracture. The heated product then drains by gravity or is gas driven to production wells. Conduction heating is probably most applicable to systems containing immobile bitumens such as tar sands and oil shale deposits and perhaps to low-permeability reservoirs containing highly viscous crudes. The mechanism also acts in combination with other thermal processes where fingering or overriding of a bed occurs. It seems probable that in at least one field test, conduction heating of this type was very influential.2 In this presentation we give a first approximation to some of the quantitative aspects of conduction heating. Marx and Langenheim3 treated a similar problem where they focused attention upon the injection interval, which spanned the total reservoir thickness. In their model, conduction heat losses to the bounding media imposed a practical limit on the calculated heated area. In the present study, however, we shall confine the injection interval to a small fraction of the reservoir thickness and assume it has no heat capacity. We therefore direct our attention to regions outside the injection interval into which the conduction of heat is beneficial. In particular, we will endeavor to locate specific isotherms in the media bounding the injection interval. Furthermore, we will construct our model to allow the thermal conductivity to vary arbitrarily with temperature. Thus the model will be applicable to underground retorting of shale where variations in thermal conductivity may be important. THEORY We consider the rock matrix to have no or, at best, a very limited permeability; consequently a

Jan 1, 1965

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

The microstructural stability of 59 carbon and low alloy steels after 34,000 hr exposure at 900' and 1050°F, including the weld heat-affected zone, is discussed. The tensile and creep rupture properties of the parent metal of many of the steels before and after 10,000 hr exposure are presented. SEAMLESS pipe has been used for many years at elevated temperatures. When seamless first began to be used, operating temperatures and pressures were relatively low and the steel produced adequately met the existing requirements. The need for knowledge of creep properties and graphitiza-tion was nonexistent. Today the requirements for tubular products have changed considerably. Operating temperatures and pressures are increasing continually and corrosion, particularly at high temperatures, presents a problem. Carbon steels have, under these conditions, certain economic advantages particularly in oil refinery use. However, the use of low alloy steels in the generation of steam power has increased appreciably due to the influence of molybdenum on creep strength and the control of graphitization with chromium. The behavior of carbon and certain low alloy steels after long periods of exposure at 900° and 1050°F (480° and 565°C) has been investigated. The steels were examined before and after 10,000 to 34,000 hr exposure. Results obtained with material exposed at 1200°F (650°C) are not presented due to the severe oxidation and resulting decarburiza-tion after long periods of exposure. The graphitization characteristics of carbon and low alloy steels are of fundamental concern to the users of these materials. This is particularly true where welded joints are employed. In order to evaluate properly the behavior of steels at elevated temperatures, it is desirable to employ not only long periods of exposure under controlled conditions, but to use material with known properties and steelmaking practices. The purpose of this investigation has been to study the microstructure of the weld and the tensile and creep rupture properties of the parent metal after long periods of exposure at elevated temperatures. In the report'.' of a previous investigation data were presented on the microstructure, impact strength, hardness, and oxidation characteristics after 10,000 hr exposure at elevated temperatures. When this investigation was planned, methods for controlling the graphitization characteristics of steel were not established and, therefore, a number of special alloy steels were included in the study. During the exposure of these steels, the influence of aluminum in accelerating the rate of graphitization and the inhibiting power of chromium were established by various investigators. Also, the vanadium-bearing steels, because of their outstanding creep properties, received attention. As a result of these developments, considerable progress has been made in the field of high temperature tubular products, and the necessity for special alloys to prevent graph-itization has been restricted largely to the use of chromium. Material Chemical analysis, deoxidation treatment, and austenitic grain size of the 59 steels discussed in this paper are shown in Table I. The steels were forged to 1x1 in. bars with the exception of steels 12B, 12DX, 12DY, 12DZ, 70, 70A, 72 to 78, 82, and 83 which were machined from heavy wall pipe. All bars were surface ground before exposure. Heat treatment before exposure is shown in Table 11. The majority of the steels included were melted in either a basic open hearth or basic electric furnace; how-

Jan 1, 1955

By V. J. Berry, J. D. Pendergrass

Well pressure transient tests provide a means for directly obtaining information about formation pressure and reservoir flow capacity. Such tests have also been proposed for determining presence and location of faults or other reservoir closures and for measuring oil in place. For mathematical convenience, most theoretical studies have considered the reservoirs to be homogeneous. Definitive information is not yet available to show whether the actual presence of nonuniformities will make pressure transient behavior different from that of a uniform reservoir. The conclusions reached from actual transient tests are questionable, therefore, insofar as they rely on the original assumption of homogeneity. One type of nonuniformity commonly assumed to exist is that of stratification. In most reservoirs the strata are thought to be in vertical communication. Equations for the transient flow of a single-phase, compressible fluid in a one-well, bounded, circular reservoir have been solved for several situations involving crossflow between multiple strata of various thicknesses and permeabilities. The results show that except for the very early flow period, which usually is too short to be analyzed, the transient performance observed at the well is substantially identical with that of a homogeneous reservoir having the same dimensions and having the same steady-state flow capacity. Thus, stratification does not adversely affect interpretation of well transient tests. This conclusion holds for all commonly encountered combinations of reservoir thickness and external radius. Deviations are observed for unusually thick reservoirs whose outer radii are relatively small. The results of these studies also show that the presence and the amount of stratification cannot be simply diagnosed from reservoir pressure transient data when there is crossflow between strata. INTRODUCTION The last decade has brought wide acceptance of the transient well pressure test for determining reservoir parameters. Following the original work of Hurst and van Everdingen,1 the mathematical theory was thoroughly explored. Numerous authors have suggested how to determine static reservoir pressure, permeability-thickness product, original oil in place and reservoir limits for different reservoir geometry. The same mathematical techniques have been used to predict the transient performance of a reservoir over a long period of time. Most of the theoretical work has been for homogeneous, isotropic systems. Some results have also been presented for a homogeneous, anisotropic reservoir.2 Petroleum reservoirs are not homogeneous. The deposition process seems to favor creation of a stratified formation. This concept is sufficiently well accepted so that the most natural extension of the transient flow theory beyond the homogeneous case is to a stratified formation. Results for a stratified reservoir with no vertical communication between layers can be obtained from the results for a homogeneous reservoir. Lefkovitz, et a1,3 have given a thorough treatment of the two-layer case. Two recent papers4,5 have treated the case of a two-layered reservoir with vertical communication or crossflow, between layers. Russell and Prats4 find that, after a relatively short time, the two-layered reservoir with crossflow exhibits a simple exponential pressure decline. From this time forward, the behavior is not distinguishable from the behavior of a homogeneous reservoir having the same steady-state flow capacity. The results of Katz and Tek 5 are equivalent. Russell and Prats4 also speculate that a multi-layered reservoir with crossflow will behave as a homogeneous system after long enough production time "... providing the contrast in kh between layers is not too great". They also suggest that, at intermediate times, "... the relative positions of the layers with respect to each other will have a great influence on the production behavior and on the time at which the previously mentioned large-time approximation might be valid". Katz and Tek5 remark upon the mathematical difficulty of treating a reservoir having many layers or strata. If relative position of the layers is also

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting' thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By H. Macpherson

Durhm has a well earned reputation for supplying some of the finest coking caals in the world. The caals, in general, vary in rank from 301 to 501/2. Durham has traditionally produced foundry coke for the major proportion of the foundries in Great Britah. Durham coals can be described as clean, soft coals, which yielded, with the old hand methods of coal getting, low ash small coal because the extraneous shale was normally harder than the coal and occurred in larger pieces. Under these conditions, with a plentiful supply of cheap labor, it used to be sufficient, at most collieries, to hand clean the large sizes of coal which could then be remixed with the untreated small coal to produce carbonization coals, ready for the coke ovens, at under 5 pct ash. With the introduction of mechanical methods of coal mining, the coal gradually required more cleaning. The first method adopted to resolve this problem was the introduction of pneumatic dry cleaners for the small coal. Although such machines had little effect on the fine coal (say below 1/8 in.), they could clean the intermediate sizes of coal. This, coupled with hand cleaning the larger sizes above 1-1/2or 2 in., resulted in a combined run-of-mine mixture below 6 pct ash, capable of maintaining the quality and reputation of the cokes produced. In more recent years, the intensification of mechanization and power loading, coupled with gradual exhaustion of the cleaner seams, has created the need for a more complete method of coal cleaning. This particularly applies in the fine sizes (say below 1/50 in.) which normally vary, under present day conditions, between 15 and 35 pct ash and are much too dirty to be included in the raw state in a carbonization mixture. This pronounced change has been accelerated because legislation controlling the dust conditions of mine airs for the prevention of pneumoconiosis has resulted in tk~e extensive use of water underground and a consequent increase in moisture content of the run-of-milie output. The presence of damp fine coal decreast the efficiency of prescreening and dry cleaners, so that this type of preparation for low ash coking coals is decreasing, although it is still used satisfactorily for industrial coals in the medium ash range. Table I shows the gradual increase in mechanization, the reduction in manpower, the increased use of explosives per ton of coal extraction, and the increase in the proportion of coal cleaned by mechanical means in Great Britain. Although similar figures are not available for Durham Div. until after the date of nationalization of the coal industry, it is probable that the increase in mechanical cleaning, particularly by dry cleaners, was more marked in the Durham collieries than elsewhere in the country. As dry clealiers were replaced by coal washeries in the Gritish ccal industry, no special attempts were made to recover the slurry, with the result that large outflows of dirty water were allowed, deposits of slurry came in to lagoons and neighboring streams, and a proportion of fine material was lost from the coking coal. This position, coupled with the higher moisture of the washed coking coal, resulted in adverse effects on coke oven throughputs and coke quality. It is now realized that the natural coal fines are an essential ingredient of coking coals in obtaining the correct coke structure in metallurgical cokes. This, together with economic pressure, led to the introduction of flocculation and filtration plants for the recovery of slurries, and later, when the ash contelits of the filter cakes were too high, to the introduction of froth flotation equipment. After this position had been reached, the tailings from the froth flotation pIants were, in many cases, still allowed to constitute an undesirable effluent. Recent legislation on river pollution has changed this picture; it is now necessary to provide a circuit which is completely closed so far as solids are concerned. The gradual increase in the coal cleaned by wet methods and froth flotation in Durham Div, is shown in Table 11. It is now an accepted feature of new Washeries that. froth flotation should be an integral part of the washing process from the initial installation of the plant.

Jan 1, 1962

By G. L. Corrigan, J. R. Coleman

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941

By Gerald Sherman

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

Jan 1, 1951

By P. K. Koh, G. C. Dunn

Si-Fe single crystals in a number of selected orientations were cold rolled 70 pct and analyzed to obtain quantitative (110) pole figures. Stable end orientations were ddetermined, and the effect of orientation on deformation behavior was investigated. WHEN single crystals are cold rolled sufficiently, they rotate into end orientations that are stable or unchanged in position with additional deformation. The end orientations of heavily cold-rolled iron crystals, positioned in holes in copper to limit lateral flow and to simulate polycrystalline conditions during deformation, were determined by Barrett and Levenson.' They found that the sum of the end orientations, a pole figure for all the crystals studied, reproduced the essential features of the cold-rolled texture of polycrystalline iron. In. an investigation of Fe-Si alloys, Barrett, Ansel, and Mehl' observed little effect of silicon content on the textures of heavily cold-rolled samples. Since alloys with less than 4 pct Si are known to have the same slip systems as iron," it seems logical to expect that they would also have the same end orientations as those for iron. Whereas Barrett and Levenson in their study of single crystals were interested in the problem of the origin of the cold-rolled texture of polycrystalline iron, the present authors are more interested in the final cold-rolled textures of single crystals of Si-Fe from the point of view of their relationship to subsequent recrystallization phenomena which will be reported in another paper. Nevertheless, such points as the tendency of an end orientation not to rotate (stability), the tendency of a pole concentration to spread out, and the tendency of the crystal to widen during cold rolling become interesting separately when the initial orientations are selected already in end orientations. Also the initial orientations having a [I101 axis parallel with the transverse direction, which include the two end orientations (111) [Ti21 and (001) [110], comprise a series that needs further clarification regarding the way such crystals rotate during deformation. Finally the present use of quantitative pole figure methods* represents an advance over the X-ray photographic method employed by Barrett and Levenson in their work on end orientations. The present investigation provides information on the cold-rolling behavior of two groups of Si-Fe crystals: 1-—crystals initially oriented in recognized end orientations for iron crystals with a [I101 direction parallel with the rolling direction, and 2— crystals initially oriented with a [I101 direction 90" to the rolling direction and in the rolling plane. For the second group, there is a 90" range between the (001) [110] orientation and the (110) [001] orientation. Since the 35" portion of this range from (110) [OOl] to (111) Di2] was included in a previous investigation," only the remaining 55" portion from (111) fii2] to (001) [I101 needs further consideration. Also, since both (111) [xi21 and (001) [I101 are end orientations for iron crystals,' there might be a critical orientation* or orientation range be- • W. W. Martin and C. G. Dunno noted that (112) [Till was such a critical orientation. tween them such that early in the deformation an orientation within this critical range splits into two orientations. Upon further deformation, these two orientations rotate to produce a final texture consisting of (001) [1101 and (111) [?i2] components. The end orientations obtained are discussed in connection with the work of Barrett and Levenson, while the observed tendency for lateral flow of crystals in these orientations is treated in terms of the theory of Hibbard and Yen.' Lateral flow according to the theory increases with deviation of the plane containing the rolling direction and the slip direction from a position perpendicular to the plane of rolling. Experimental Procedure Single crystals in sheet form with preselected orientations were prepared by methods that have been described elsewhere." Three lots designated A, B,

Jan 1, 1956

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.' Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,' even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By P. L. De Bruyn, R. J. Charles

THE transfer of kinetic energy of translation into other forms of energy by impact is a fundamental process in most crushing and grinding operations. During and after the impact process the original source energy may be accounted for in any of the following possible forms: 1) Kinetic energy of translation of both the impacted and impacting objects. 2) Kinetic energy of vibration of the components of the impact system. 3) Potential energy as strain energy of the components of the system or in the form of residual stresses. 4) Heat generated by internal friction during plastic deformation or during damping of elastic waves. 5) New surface energy of fractured materials. At any instant during the impact process only the strain energy of the components of the system can contribute directly to the brittle fracture process. If fracture is the desired result, as in comminution, it would seem advantageous to choose or arrange the conditions of impact so that a maximum amount of the original kinetic energy could be converted to strain energy at some moment during a single impact. The present work deals with determination of these desirable conditions for a simple case of impact and application of the principles involved to general cases of impact. Experimental Method: Longitudinal impact of a rod with a fixed end was chosen as the impact system for investigation. The rod was mounted horizontally and the fixed end was formed by butting one end of the rod against a rigidly mounted steel anvil. The rod, of pyrex glass, was 10 in. long by 1 in. diam with both ends rounded to a 6 in. radius. The rounded ends permitted reproducible impacts on the free end of the rod and assured a symmetrical fixed end. Pyrex was selected as the rod material because of the marked elastic properties of such glass and the similarity of fracture between pyrex and many materials encountered in crushing and grinding operations. The frequency of natural longitudinal oscillation of the rod was 10 kc, and thus simple electronic equipment could be used for observation of strain changes occurring in the rod at this frequency. As shown in Fig. 1, impacts on the free end of the rod were obtained either by a pendulum device or by a spring-loaded gun. Relatively heavy hammers (100 to 600 g) of mild steel were used in the pendu- lum impacts, while fairly light projectiles (20 to 80 g) were fired from the spring-loaded gun. One of the main objects of the experimental work was to obtain the strain-time history of the rod as a function of the mass and kinetic energy of the impacting hammers. For this purpose a technique involving wire resistance strain gages and a recording oscilloscope was employed. Five gages were applied at equidistant sections along the rod, and by means of a switching arrangement the strain-time history at any section, and for any impact, could be obtained in the form of an oscillograph with a time base. The equation relating strain and voltage change across a strain gage through which a constant current is flowing is as follows: e = ?v/iRF [1] ? = strain, ?v = voltage change, i = gage current, R = gage resistance, and F = gage factor (from manufacturer's data — SRA type, Baldwin Lima Corp.). With the above equation an oscillograph depicting voltage change vs time on a single trace can be converted directly to a strain-time diagram if a calibration of the vertical response on the oscilloscope screen for specific voltage inputs is available. In the present case the calibration was obtained by photographing precisely known audio frequency voltages on the same oscillograph as that on which a voltage-time trace from a strain gage had been made. Synchronization of the beginning of the single trace with the beginning of the impact was accomplished by permitting contact of the impacting objects to close an electrical circuit from which a voltage pulse, sufficient to initiate the trace, was obtained. The struck end of the rod was lightly silvered for purposes of electrical conduction so that it would form one of the electrical contacts. Markers every 100 micro-seconds on the traces served for a time base calibration. Determinations of the kinetic energies of translation prior to impact were made in the case of the pendulum hammers by measuring the height of fall of the hammer and in the case of the projectiles by measuring the exit velocity from the gun barrel by means of an electrical circuit employing light sources, slits, and phototubes.' During the experimental work it became evident that the time of contact between the impacting object and the rod was an important variable in the impact process. Measurements of the times of contact were made, therefore, for every impact for which a strain-time record was obtained. The time of contact was determined by permitting the impacting components, when in contact, to act as a closed switch and discharge a condenser at relatively constant voltage. The discharge was observed and photographed with a time base on the oscilloscope screen.

Jan 1, 1957

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By N. De Nevers

A calculation method has been developed for carbonated water flooding. This method takes into account the effects of oil viscosity reduction and oil swelling, due to carbon dioxide transferred to the reservoir oil from the carbonated flood water. It shows the effect of changes in carbonation pressure and carbonated water slug size. The method is based on a Buckley-Leverett-type linear flow model. The mathematical approach is similar to that developed by Welge, et al, for enriched gas drives. However, it contains a very important advance over the previous papers in its solution to the problem of injection of a "slug" of carbonated water rather than continuous injection of fluid of constant composition. The method also shows the chromatographic nature of the transport of Co 2 in a carbonated water flood. Sample calculations indicate that viscosity reduction is the most important source of incremental oil recovery. Swelling contributes to a lesser extent. Raising the carbonation pressure increases recovery, but this effect diminishes as pressure is increased. increasing the slug size also increases recovery, but again this effect diminishes as slug size is increased. INTRODUCTION In recent years there has been considerable interest in carbonated water flooding as a secondary recovery method. Several carbonated waterflood field tests are now in progress.1'3 Yet there is no published method for predicting the results of a carbonated water flood. This paper presents a method for predicting the oil recovery for ; carbonated water flood. In a carbonated water flood. a carbonated water slug is injected into the reservoir. Then this slug is driven forward by injecting plain water behind it. The field operator must choose the carbonated water slug size and the CO2:water ratio in the slug. The calculation method presented here shows the effects of both slug size and CO2:water ratio on oil recovery. The calculation assumes that the addition of carbon dioxide to flood water increases the oil recovery by two mechanisms: 1. Carbon dioxide transfers from the flood water to the oil, thereby reducing the viscosity of the oil. At the lower viscosity, the oil flows more readily and is more easily swept out by flood water. 2. The carbon dioxide which transfers to the oil phase causes the oil phase to swell. Assume that the residual oil saturation (volume per cent of pore space) is the same whether the oil is carbonated or not. Then the same volume will contain less stock tank oil if it is carbonated, due to oil swelling. The plain water driving the carbonated water slug forward will strip the CO2 out of this residual oil., causing this oil to shrink. This swelling-followed-by-shrinking leaves behind a lower residual oil saturation than would have been left behind by a plain water flood. Since some oils swell to almost twice their original volume at reasonable CO2 pressures, this effect may be large. Two additional benefits sometimes claimed for carbonated water flooding are: 1. Adding CO2 to flood water greatly increases the water injectivity in some cases.1 (Injectivity = BPD of water injected/ft of sand x differential bottom-hole pressure, psi.) CO2 forms a weak acid in water; injecting carbonated water is, therefore, somewhat like acid treating. If a formation responds to acid treating, it will probably have a higher injectivity for carbonated water than for plain water. Although the increased injectivity increases the profitability of a carbonated water flood over a plain water flood, it does not change the production curve based on total fluid injected. Therefore, the method presented here does not show any effect of increased injectivity. 2. It is claimed in one patent4 that carbon dioxide will react with some constituents of the oil to form detergents. These detergents are expected to increase the oil recovery. There is little data available to support this idea. The calculation method presented here takes no credit for extra oil recovery due to the formation of any such detergents.

Jan 1, 1965

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

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

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

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

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

Jan 1, 1956

By Nicholas J. Grant, Robert H. Kane, Bill C. Geissen

The platinum-rich section of the Ta-Pt Phase diagram was worked out by metallographic and X-ray techniques, using twenty alloys; solidus temperatures and solid solubilities were determined. Besides s phase, four intermediate stoi-chiometric phases were found: TaPt (high-temperatzrre phase, structure unknown); TaPt2 (ortho-rhomhic, new type); a TaPt3 (orthorhombic, TiCu3 type); ß TaPf3 (monoclinic, new type). TaPt2 and TaPt3 melt congmentlv; two eutectic, two beritec-tic, and one eutectoid reactions occur in the inuestigated range. THE Ta-Pt system was examined as part of a study of the phase diagrams and the intermediate phases of niobium and tantalum with Group VIII transition metals. Since the main scope of this work was the relation among the ordered close-packed phases occurring in the concentration range from AB to AB3 (A = Nb, Ta; B = Pd, Pt, and so forth), only the platinum-rich side of the diagram was worked out thoroughly, while spot checks were made to determine the approximate outline of the tantalum-rich portion. The system has not been thoroughly treated in the literature; Greenfield and Beck1 in their survey of refractory metal intermediate phases found a o phase between -18 and 37 at. pct Pt which coexists at higher platinum concentrations with an unidentified intermediate phase. Browning2 worked on the range between 55 and 100 at. pct Pt; however, this preliminary study did not cover temperatures >1500°C, and included no conclusive crystallo-graphic data. More recently, a study of the platinum-rich section of the Ta-Pt system has been carried out by Ray,3 while Hartley, Parsons, and steedly4 have studied the tantalum-rich section. The crystal structures of TaPt2, a TaPt3, ß TaPt3, and others have been reported in abstracted form by Giessen and Grant.5 EXPERIMENTAL METHODS The methods of alloy preparation and processing and of the metallographic and X-ray procedures follow very closely those described by Ritter, Giessen, and rant' for other refractory metal-noble metal systems, and will not be repeated except where significant differences exist. Starting materials were: tantalum rod of 99.95 pct purity, supplied by National Research Corp., and platinum sponge 99.9 pct, supplied by The International Nickel Co. An oxygen analysis of the tantalum rod showed 30 ppm O; other impurities were C, N, Si, Nb, Mo, none of these exceeding 50 ppm, and 100 ppm W. Homogeneous buttons were readily prepared as follows: ingots of 5 g were weighed and arc-melted under welding grade argon, followed by two remelts after inverting the button. Between 40 and 100 at. pct Pt, weight losses during the first melt rarely exceeded 0.1 pct, in which case the alloy was rejected, and were nil on subsequent remelts. Since the vapor pressure of platinum far exceeds that of tantalum, the small evaporation loss could be assumed to consist of platinum; therefore, a corresponding amount of platinum was added on the second melt. Since it was confirmed on pure tantalum samples that no weight gain through oxygen or impurity pickup occurs (see Ref. 71, it could be assumed that the uncertainty in the composition did not exceed ±0.1 at. pct for the range 40 to 100 at. pct Pt. For the four control melts from 0 to 40 at. pct Pt, an error of ±0.5 at. pct was calculated. Microscopic examination of the whole buttons after melting showed no inhomogeneity other than local coring. This was eliminated by a homogenization heat treatment. A total of twenty-three alloys were prepared. Heat treatments were carried out in a tantalum

Jan 1, 1965