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By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.' This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.'," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01' the gas at the displacement front by evaporation of the C, - C,

By E. C. Barfield, D. G. McCarty

Two-dimensional analyses offer considerable promise in providing the basic information required to effect more precise control of petroleum reservoir performance. This paper describes a method for conducting some engineering analyses of this type using a high-qreed digital computer. The general approach is to (I) develop a representative numerical model of the reservoir and (2) employ a suitable numerical technique to solve the basic equation of flow and to develop the required engineering information for the particular case represented by the model. This technique has been used to calculate pattern performance in connection with several field projects involving water injection into oil reservoirs. This type of analysis involves sequentially (I) calculating the pres-' sure distribution in the reservoir and (2) tracking the progress of the interface between the displaced and displacing fluids in a step-wise manner to provide a depletion history of the operation. The particular analysis presented in this discussion is subject to the restriction that the mobility of the displaced and displacing fluids be equal and assumes that the fluids are incompressible and that gravity and capillary pressure do not affect the shape of the flood pattern. Complete two-dimensional .flexibility is maintained with regard to definition of reservoir rock and fluid characteristics, placement of physical restrains and boundary conditions, investigation of flow characteristics in the reservoir, and movement of the displaced and displacing fluid interface. The results of these studies indicate that the highspeed digital computer is well suited for conducting reservoir performance studies in two-space dimensions and that dependable numerical techniques are available for making such analyses. INTRODUCTION One of the problems facing petroleum engineers is that of providing more precise engineering control over reservoir operations at all stages during the depletion cycle. The most direct approach to this problem is to simulate the reservoir with some type of physical or mathematical model and use the information developed from the behavior of the prototype to predict the performance of the actual reservoir. This principle is, of course, not new, and a variety of simulation techniques have been developed to provide information on the behavior of oil and gas reservoirs. One straightforward refinement of present reservoir analysis techniques is the progress from one-dimensional reservoir models to those where the reservoir can be represented in two- and three-space dimensions. Multidimensional reservoir analyses are desired in order to show not only what is happening in the reservoir but in addition to show where in the reservoir the various phenomena of interest are occurring. Thus far, two-dimensional analyses have been confined predominantly to potentiometric and electrolytic model studies. However, when large numbers of wells are involved and where large-scale models are required, such problems become very tedious and instrumentation problems become acute." It is possible through use of numerical methods and general purpose digital computers to avoid many of the instrumentation difficulties and to relax some of the restrictions of previous techniques. The purpose of this paper is to discuss some recent experiences with the use of high-speed digital computers for predicting pattern performance in fluid injection operations and to describe the numerical procedures which have been used for making such analyses. THE NUMERICAL MODEL The problem of representing the reservoir with an appropriate numerical model is composed of at least two important considerations. The first requires that an adequate description of the reservoir mechanism be formulated in the form of the basic differential equation describing the process. The second consideration is definition of the physical characteristics of the reservoir. The latter requires that representative basic data be obtained, examined, and interpreted to provide sufficient detailed definition of the pertinent physical properties throughout the system. The Differential Equation One of the basic assumptions made for the purpose of performing the two-dimensional studies being dis-

By Albert G. Zima

According to recently puhlished statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet. Drill Tools Modern rotary drilling tools are the product of ingenious design and careful selection and adaptation of materials used in their construction. They must withstand terrific abrasion and, because of their compactness, must be designed to resist exceedingly high unit stresses. In bits, core drills and reamers, the bodies are made of either forged or cast alloy steels, heat-treated to develop a combination of high strength and toughness. To provide sufficient strength to the threaded portions and to protect the threads from distortion or damage, the box or pin sections of the tools are hardened to approximately 310 to 330 Brine11 hardness number. Drill and reamer cutters are generally of the movable type; i.e., serrated cones, cylinders or disks, which can readily be replaced when

Jan 1, 1935

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of ternary and quaternary additions of aluminum, oxygen, and carbon on the mechanical properties of high-purity titanium-molybdenum alloys were studied for several microstructural conditions. Heat treatments were designed to produce 1) ß-quenched, 2) equiaxed ß) transformed (acicular) and 4) stabilized -P microstructures. Tension, impact, and hardness tests were performed. Transformations from the ß phase were followed by hardness measurements and metallography. The ß-to-w transformation was slowed by aluminum additions; carbon and oxygen additions increased the transformation rate. In addition to solid-solution strengthening, these solutes may increase or decrease strength by altering the /3 transformation kinetics. Aluminum additions promote the formation of strain-induced martensite, and lower yield strengths at compositions near 12 pct molybdenum.. a-P alloys are more ductile with equiaxed than with transformed microstructures. High strength levels can be reached by aging in many cases. Strength levels of the aged specimens usually are lowered slightly by straining prior to aging. ALLOYS of molybdenum with titanium form an iso-morphous alloy system which has been the subject of several investigations. Additions of substitu-tional and interstitial -stabilizing elements provide means of improving mechanical strength and con- trolling the heat-treatment response of the binary alloys. The work reported here forms a part of a continued study of the effects of microstructure on the mechanical properties of high-purity titanium alloys. Previous papers have considered the various binary alloys (Ti-Mo, Ti-Al, Ti-C, and Ti-0) that form the bases for the ternary and quaternary alloys included here. The compositions were selected to correspond with the previous binary alloys. Further, the high purity of the alloying components was maintained, so that direct comparisons with earlier work can be made. The total research program included a large number of compositional, microstructural, and testing variables. The data reported here have been selected to provide a reasonably complete and representative summary of the results. The reader is referred to the original Air Force Report for a complete tabulation of the results. EXPERIMENTAL PROCEDURES All the alloys used in this work were prepared from high-purity electrolytic titanium produced by the U.S. Bureau of Mines. A typical furnished analysis showed the following impurities in wt pct, balance This analysis is equivalent to that of iodide-refined titanium. In addition, hardness, tensile, and impact tests made using unalloyed electrolytic titanium showed it to have properties equivalent to those obtained with iodide titanium and suitable for these studies of high-purity base alloys.

Jan 1, 1962

By H. T. Clark, S. Feigenbaum

THE importance of measuring the temperature of molten steel in the open-hearth furnace has been recognized for many years. Poor temperature control may be costly to steelmaking operations and lead to a lowered quality of the steel. Low or excessive temperatures may shorten the life of the furnace, ladles and molds. Rates of reactions in the furnace and efficiencies of deoxidizers are known to change materially with a change in the temperature of the metal and slag. Ladle skulls and mold and stool stickers cause steel to be scrapped instead of being converted into useful products. Finally, the structure, segregation and surface condition of ingots are affected by the teeming temperature. Mill investigations of the effect of bath temperature upon steelmaking operations have been largely qualitative in character, based upon observations by practical melting men. The physical chemist has used the empirical information available and has reached reasonable and useful conclusions with respect to the various melting processes. The introduction of a reliable direct- reading pyrometer will permit accurate quantitative evaluation of the effects of temperature and should furnish a more rational basis for study of the thermo- chemistry of steelmaking. The problem is not merely one of making a small number of temperature measurements in the open-hearth furnace. This has been done by several methods to a degree of precision that was apparently satisfactory. Considerable effort by a number of investigators has been directed rather to the development of an open- hearth bath pyrometer that would be both accurate and practical for routine measurements. To be practical, the pyrometer should be inexpensive to operate; that is, the installation, operating and maintenance costs should be exceeded by the tangible benefits to the open-hearth operator. Temperatures from 2800° to 3100°F. are encountered in the open-hearth furnace. The surface of the molten metal is covered by several inches of slag, which prevents direct observation of the metal surface for optical or radiation measurements. Both slag and metal are highly reactive at these temperatures and will attack to a greater or lesser extent any material immersed in them. Adequate protection of thermocouples, which of necessity must be brought to the temperature of the bath, has generally resulted in a large, heavy assembly made up of .brittle materials, unsuited for handling on the open-hearth floor. The lie of the equipment was short and maintenance was an important consideration. EARLIER WORK Any one of a number of physical proper- ties of liquid steel could conceivably be used as a basis for temperature measurement. Efforts to the present time, however, have been confined largely to measuring either the thermal electromotive force generated between two dissimilar materials immersed in the steel or the intensity of radiation from the surface of the steel. These

Jan 1, 1946

By A. H. Daane, J. F. Haefling

The limits of miscibility in some of the uranium rare-earth alloy systems have been determined in the temperature range 1000°to 1250°C. The solubilities of lanthanum and cerium in uranium are greater than those of the remaining rare earths by a factor of more than two. The solubility of uranium is greater in cerium, braseodymium, and neodymium than in the other rare-earth metals studied. The values found in this study are in qualitative agreement with those which might be expected if the solubility rules of Hildebrand and Scott are applicable. AS interest in nuclear reactors intensifies, many new types of fuels are being suggested in attempts to improve the economics of some of the proposed reactor schemes. To remove some of the difficulties inherent in the use of solid-fuel elements and their reprocessing, many types of liquid-metal reactors have been suggested. One of the more attractive features of several of these reactor concepts is that they include a continuous or semicontinuous process for the extraction of fission products and "bred" fissionable materials from the fuel, utilizing immiscible metal extractants. This would enable a much higher burn-up of fissionable material to be achieved and would present a very attractive economic picture. Several studies have been reported on equilibrium systems in which there exists a high degree of immiscibility between uranium and another metal that might be used as an extractant in such a processing scheme.' Two of these systems in which a high degree of immiscibility exists are those of uranium with the two rare-earth metals, lanthanum, and cerium. Since the rare earths constitute a significant fraction of the fission products, their removal is of prime importance. It is reasonable to believe that this might be accomplished by equilibrating a rare-earth phase with the contaminated uranium fuel in the liquid state. In order to make a more complete study of those systems which would be of interest either as extractants in a liquid-liquid extraction process, or as fission products formed in the fuel, the alloy systems of uranium with lanthanum, cerium, praseodymium, neodymium, and samarium were studied in some detail in the temperature range 1000" to 1250°C; less detailed studies were made with the other rare earths. In addition to being of value to the reactor program, the data obtained in this study should be of help in making a study of the role played by the electronic structures of metals in determining the nature of metallic solutions. The unique electronic structures of the rare-earth elements make them particularly interesting in this respect. EXPERIMENTAL The usual procedure for a solubility determination was to seal equal volumes of uranium and the particular rare earth in a tantalum crucible under an atmosphere of helium; this crucible was then sealed in a stainless steel jacket in an atmosphere of helium. These samples were equilibrated by repeated inverting of the crucibles in a furnace for 15 min at the desired temperature, left in an upright position for 15 min to permit separation of the two phases, and then quenched under a stream of water. In some runs the temperature of the furnace was held 50' to 100°C above the desired quenching temperature while inverting in order to insure good mixing. However, it was found that above 1200°C the crucibles were subject to failure and for these runs the furnace temperature was not raised above the desired quenching temperature. A small amount of tantalum was dissolved in the uranium and the rare earths in these runs, a maximum of 3 wt pct in the uranium phase at 1250°C and up to 1 wt pct in the rare-earth phase at this temperature. On cooling, the major portion of this tantalum precipitated as primary tantalum crystals. Any residual tantalum would probably have a negligible effect on the mutual solubility of uranium and the rare earths in each other. Samples for analysis were cut from each phase with an abrasive cutting wheel; the region near the interface between the two metals was carefully avoided. In the case of the rare earths with melting points above 1250°C no solubility data were taken on the rare-earth phase since this phase could not have achieved equilibrium in a reasonable length of time. (For the same reason no data were taken on the uranium phase below its melting point of 1132°C.) Equilibrium appeared to have been reached in the uranium phase in these cases although the rare-earth phase had not melted. To verify this, samples were melted together in an arc furnace similar to that described by Kroll.2 These samples were sub-

Jan 1, 1960

By H. Leslie Bullock

From aluminum to zirconium, the quantitative preponderance of quartz as a gangue material is well recognized. lf this material is to be efficiently removed, its variations must be understood. Variations with temperature are especially important. Too little attention has been given to the thermal polarization of quartz. Under closely controlled conditions, electrostatic upgrading is very reliable. For efficient separation, contact charges must be fostered and charges due to radiation, surface coatings, or thermal polarization avoided. This paper lists thermal transition points of quartz and shows their effect on actual separations. Simple separation tests with all factors except temperature held constant are recommended for determining transition points. With silica making up more than 27% of the earth's crust, its oxides comprising more than 59% of all igneous rocks, and quartz accounting for most of the main free oxides, the mining engineer is in constant contact with quartz, which may occur as a valuable mineral to be purified or, far more frequently, as a gangue material to be removed as completely and economically as possible. As a means of effecting such purification or removal, dry beneficiation is becoming more and more desirable owing to local water scarcities, wet waste disposal problems, or freezing conditions. One method that has been gaining particularly rapid acceptance is electrostatic beneficiation, or the separation of dry free-flowing materials by means of opposite surface charges, differences in potential, or differences in conductivity. Electrostatic beneficiation dates back to the 1870's, but only in recent years have newly developed methods and apparatus and a growing knowledge of solid-state physics widened the field for its economical application. Because the term "electrostatic beneficiation" has been rather loosely used in the literature, it has come to include both electrostatic and electrodynamic procedures. Attracting type separators, however, in which oper- ation is based on differences of surface charge or potential, are truly electrostatic, because the separation occurs in a substantially static field set up between oppositely charged surfaces. Separations with this type of equipment may occur at potentials as low as 1000 v and seldom require potentials as high as 30,000 v. In the new contact charge dielectric separators1 the variation in charge is produced by continuous contact and separation of the particles in the moving feed stream and these charges are fostered by the use of non-conducting support and feed surfaces and by handling the feed in the form of streams of appreciable depth. This favors uniformity of feed and allows higher production rates. The distinctive surface charge differences are set up on the separation of the particles according to Coehn's Law,2 which states that equal and opposite charges are generated on the separation of any two materials in contact and that the substance having the highest dielectric constant will be positively charged. The basic contact charge concept is reliable, but all electrical charges are transient and modified by the electrical conditions of the surroundings. Pyro-electric, photoelectric and radiant effects may modify or totally destroy the contact charges necessary for efficient separation, or contact with conducting surfaces may neutralize them. Such hostile conditions must be carefully guarded against, since they have led to many costly failures in the past. The most consistent difference in surface charges to insure good separation is produced by repeated uniform contact and separation of particles in the moving stream. The thickness of the feed stream possible with this method reduces the effect of contact with the supporting surfaces, but as some contact is inevitable, the best results may be assured by having the dielectric constants of the supporting surfaces between the dielectric constants of the substances to be separated. In general, the hard smooth surface of quartz makes it an ideal substance for electrostatic separation from most minerals. For instance, with calcite, starting with a feed containing 1.9% acid insolubles, one can produce a concentrate containing 0.30% acid insolubles with a tailings containing 21.7% acid insolubles and a yield of 92.8%. The color can be held at 92 or above and the tint at 1.7 or lower. Working with specularite iron ore, laboratory work has given a concentrate of 68.8% Fe., with an iron unit recovery of 96.7%. Excellent results are also in pros-

Jan 1, 1969

By H. S. Choi, I. Iwasaki

The effect of temperature as a parameter in ore flotation has not been systematically studied, although for some ores it has been known for many years that selectivity and grade of concentrates can be improved by conditioning or flotation at moderately or substantially elevated temperatures. In 1934 Coghill and Clemmer' stated that "elevated temperature seems to make hard water more tolerable" in soap flotation, and a cursory examination of the literature indicates that some earlier investigators were aware of beneficial results obtained by floating above room or mill-water temperatures. Tartaron,2 Mitchell et aL.,3 and particularly Hamilton et al.' have shown that high pulp temperatures give high recovery and selectivity in soap flotation of fluorite from a variety of gangue minerals. As a result of the work of these and of other investigators, high-temperature flotation has been successfully applied to industrial flotation of fluorite. Falconer" stated: "The use of high temperature conditioning (above 35°C and preferably above 60°C) in connection with the soap flotation of nonsulphide ores, as covered in B. Kalinowski's French Patent No. 847,-215, Dec. 7, 1938, is claimed to provide more intense activation, better separation of values from gangue, and reduction in quantity of reagents." The various investigations quoted above clearly demonstrate the improvements to be realized by increasing the temperature at which fluorite is floated, and it is surprising that little or no information has been published on systematic investigation of the same method as applied to other ores. The present article describes comparative results obtained at room temperature and at elevated temperatures by otherwise conventional flotation of iron ores, by single-mineral flotation in the Hallimond tube, and by contact-angle measurements. It is not the purpose of this article to evaluate the commercial feasibility of high-temperature flotation of iron ores, although preliminary calculations show that the cost should not be excessive and that the gains to be realized may well outweigh the extra cost of heating the pulp. LABORATORY FLOTATION TESTS Experimental: All flotation tests reported in this article that use a laboratory Fagergren cell were made on ore A (either containing the primary slimes or deslimed at 20µ as specified) following the preparatory procedures described elsewhere- or this particular ore. Ore A contained hematite, goethite (limonite), quartz, chert, and minor quantities of magnetite. Confirmatory tests made on other ores show that the same general principles apply to ores of similar mineralogy and structure. Conditioning was performed by adding the collector, as a soap, to the vigorously stirred and heated pulp. Conditioning time was 5 min, the pulp contained 60 pct solids, and the equivalent of 0.5 Ib of fatty acid was added per ton of original (unde-slimed) ore. The pH of the pulps ranged from 6.8 to 7.1 (25°C measurement) during conditioning. The pH was adjusted in the flotation cell by addition of either NaOH or H2SO4, the values reported being those of the pulp cooled to 25°C. During conditioning and flotation the pulp temperatures were controlled within l° to 2° by immersion of Variac-controlled Calrod elements in the conditioning beaker and in the cell, and by the use of water, heated to the appropriate temperature, for transferring pulp, adjusting pulp volume, and washing. Selectivity indexes have been calculated on the same basis as those reported in the article by Cooke, Iwasaki, and Choi." Results: Table I gives the results obtained by floating deslimed ore A with pure oleic acid at 25" and 50°C, and Fig. 1 shows the selectivity indexes plotted against pH of flotation. Inspection of Table I

Jan 1, 1961

By Paul A. Farrar, Harold Margolin

The Ti-Al-V system has been delineated from 50 to 100 wt pct Ti and front 600 to 1400°C by X-ray and ntetallographic techniques. Isothermal sections were delineated at 600, 700, 800, 900, 1000, 1100, 1200, 1300, and 1400°C. X-ray and metallographic evidence indicated the presence of two phases and in addition to those reported by previous investigators of the ternary system'-3. T HE titanium-rich region of the Ti-Al-V system as originally proposed by Rausch et UZ, and Jordan and Duwez3 was based on the binary Ti-Al diagram as proposed by Bumps et uZ. As additional phases have been shown to exist5-' in the region previously thought to be all a, the titanium-rich region of the Ti-Al-V system is open to serious question. Therefore, in order to determine the effect of the indicated changes in the Binary Ti-Al system on the ternary Ti-Al-V system the present investigation was initiated. EXPERIMENTAL PROCEDURE The experimental procedures in this investigation are the standard techniques used in the study of titanium-alloy systems which have been described in detail previously.1° Consequently, only details pertinent to the present work are discussed. The alloys employed for the delineation of this system were prepared from titanium obtained from the Bureau of Mines (73 BHN) 99.99 pct Al and 99.7 pct V, by the consumable arc-melting technique. The titanium was premelted into buttons of 25 g because spattering during the first melt caused uncontrollable loss of alloying constituents. Typical analyses of the material used have been reported elsewhere Attempts to hot roll the alloys prior to heat treatment were made on the first series of alloys prepared, but as the area of extensive hot workability was fairly restricted, see Table I, this practice was discontinued. The times of isothermal annealing are given in Table 11. A preliminary heat treatment of 96 hr at 1000°C was used prior to heat treatment at lower temperatures. The standard techniques used for polishing specimens involved belt-grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch. In the low-alloy region it was found that the oRo etch, developed by Ence and Margolin,o gave better contrast between phases. Where this procedure did not differentiate between phases clearly, the method of stain etching developed by Ence and was used. It has been previously reported15 that filing of titanium alloys is not desirable for producing X-ray powders, since the powder becomes contaminated by the file material. Therefore, for those samples not brittle enough to Crush, the procedure described below was used. The specimen was wrapped in molybdenum sheet and placed in a vacuum system and evacuated to 0.03 p. Palladium-pur if ied hydrogen was then admitted to the system until a partial pressure of 5o Cm of H was reached. The specimen was heated in the system to the temperature of original heat treatment and was slowly cooled over a period of 3 hr to 400°C while the partial pressure of hydrogen was maintained. The sample was removed from the system after it had completely cooled and was crushed to a powder of 230 to 270 mesh. The powder, wrapped in molybdenum sheet, was dehydrogenated at the temperature of original heat treatment until a partial pressure of 0.03 p was maintained in the system for at least 1/2 hr. The tube containing the powders was quenched in iced brine while still connected to the vacuum system. After dehydrogenation, the powder, except for the

Jan 1, 1962

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By T. E. Davidson, A. P. Lee

It is known from the early work of Bridgman that the two lowest-pressure transitions (I-II and II-III) are accompanied by substantial and abrupt changes in resistivity and Volume. However, unlike the temperature -induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of the pressure-in&ced transitions. This current work involves an examination of the structural and transformation characteristics of the bismuth I-II and II-III transitions under hydrostatic pressures. The relationship of initial structure to the transformation pressure, rate, resistivity change, and resultant structure is discussed. It is shown that the transition pressure and transformation rate are independent of the presence of grain boundaries and associated anisotropy-induced deformation. An observed hysteresis in both the I-II and II-III transitions is shown. BISMUTH is one of the most interesting of the elements exhibiting pressure-induced polymorphs since it undergoes several allotropic transformations at pressures below 90,000 atm. It is known from the early work of bridman1,2 that the two lowest-pressure transitions (1-11 and 11-111) are accompanied by substantial and abrupt changes in resistance and volume. However, unlike the temperature-induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of these pressure-induced transitions. It is the purpose of this work to examine some of the structural and transformation characteristics of the bismuth 1-11 and 11-111 transitions under hydrostatic pressures. Another interesting characteristic of bismuth is that, in its polycrystalline form, hydrostatic pressures of sufficient magnitude will induce severe progressive plastic deformation in the region of the grain boundaries.3 This deformation, which has also been observed in several other metals, is attributed to the high degree of anisotropy in the linear compressibility of bismuth, resulting in shear stresses in the grain boundaries when it is exposed to hydrostatic pressure. Most thermally induced allotropic transformations in metals, whether of the diffusionless ather-ma1 (martensitic) or isothermal nucleation and growth types, are dependent upon structure and prior history,4 viz., grain boundaries, deformation, and so forth. One logically wonders then whether the transformation characteristics of the pressure-induced polymorphs in bismuth might also depend upon initial structure, particularly with respect to the presence of grain boundaries and associated plastic deformation. In this investigation, the role of grain boundaries and plastic deformation on the characteristics of the bismuth I-II and 11-111 transitions will be established. The rather unique residual microstruc-tural changes associated with these transitions will be presented and discussed. The occurrence of a measurable hysteresis in both the I-II and 11-111 transitions will be demonstrated. The type of transformation mechanism based on the observed transformation rate will be discussed. EXPERIMENTAL PROCEDURE A) Apparatus. The hydrostatic pressure system utilized in this investigation is similar to that previously reported by Bridgman' and Birch and Robertson,5 and has been previously described.3 For the purpose of this work, the pressure medium utilized was a 1:l mixture of pentane and isopentane. Pressure measurement was by means of a manganin coil in conjunction with a Foxboro Recorder. The manganin coil was mounted in the bottom closure and inserted inside the pressure cavity. Based on calibration against a controlled clearance piston gage at approximately 10,000 atm, the estimated error in the pressure measurement was +2 pct. Assuming the nonlinearity in the pressure coefficient of resistivity between 10,000 and 28,000 atm to be not greater than 1 pct, then the estimated error in the range of the I-II and 11-111 transitions was +3 pct. B) specimen Material and Preparation. The bismuth utilized throughout this investigation was of

Jan 1, 1964

By C. E. Hottman, R. K. Johnson

Fluid pressure within the pore space of shales can be determined by using data obtained from both acoustic and resistivity logs. The method involves establishing relationships between the common logarithm of shale transit time or shale resistivity and depth for hydrostatic-pres-sure formations. On a plot of transit time vs depth, a linear relationship is generally observed, whereas on a plot of resistivity vs depth, a nonlinear trend exists. Divergence of observed transit time or resistivity values from those obtained from established normal compaction trends rinder hydrostatic pressure conditions is a measure of the pore fluid pressure in the shale and, thus, in adjacent isolated permeable formations. This relationship has been empirically established with actual pressure measurements in adjacent permeable formations. The use of these data and this method permits the interpretation of fluid pres.rure from acoustic and resistivity measurements with an accuracy of approximately 0.04 psilft, or about 400 psi at 10,000 ft. The standard deviation for the resistivity method is 0.022 psi/ft, and for the acoustic method 0.020 psi/ft. Knowledge of the first occurrence of overpressures, and of the precise pressure-depth relationship in a geologic province, enab1es improvements in drilling techniques, casing progroms, completion methods and reservoir evalzmtions. INTRODUCTION CENKRAL STATEMENT Operators engaged in the search for and production of hydrocarbon reserves in Tertiary basins are more and more frequently confronted with complications associated with over pressured (abnormally high fluid pressure) formations. This is particularly true in the Texas-Louisiana Gulf Coast area. The problems associated with these formations are of direct concern to the combined activities of all phases of operations, i.e., geophysical, drilling, geological and petroleum engineering.' - Knowledge of the pressure distribution of a given area of operations would greatly reduce the magnitude of many of these complexities and in some cases would completely eliminate specific problems. his pape; presents techniques developed for estimating formation pressures from interpretations of acoustic and electric log data. Specifically: the acoustical and electrical properties of shales, reflected by conventional acoustic and electrical surveys, can be used to infer certain reservoir properties, such as formation pressure, at any level in a well. It has been possible to develop these techniques because of a firm understanding of the basic principles that govern and apply to such overpressured provinces. NORMAL PRESSUKES Normal pressures refer to formation pressures which are approximately equal to the hydrostatic head of a column of water of equal depth. If the formations were opened to the atmosphere, a column of water from the ground surface to the subsurface formation depth would balance the formation pressure. On the Gulf Coast, the shallow, predominantly sand formations contain fluids which are under hydrostatic pressure. These formations are said to be normally pressured or to have a normal pressure gradient.* Experience has shown that the normal pressure gradient on the Gulf Coast is approximately 0.465 psi/ft of depth. OVERPRESSURES Formations with pressures higher than hydrostatic are encountered at varying depths in many areas. These formations are referred to as being abnormally pressured, abnormally high pressured, or overpressured. Formation pressures up to twice the hydrostatic pressure have been observed. These formations require extreme care and much expense to drill and to exploit. COMPACTION-FLUID PRESSURE RELATIONS THEORY The generation of overpressured formations in Tertiary sections of the Gulf Coast and several other Tertiary sedimentary basins is, in general terms, considered to be primarily the result of compaction phenomena.' This portion of the paper presents a brief review of the theory which associates compaction and fluid pressure relations, and should thus provide the necessary background for an understanding of the techniques presented. See Hubbert and Rubey' for a more comprehensive treatment of this subject. The theory of the consolidation of a water-saturated clay' has been well established by workers in soil mechanics. The concept is explained by a model with perforated metal plates separated by metal springs and water and enclosed in a cylindrical tube. Fig. 1 is a schematic representation of such a model (see Ref. 5, Fig. 27, page 74). The springs simulate communication between clay particles, and the plates simulate the clay particles. Mano-

Jan 1, 1966

By J. L. Huitt, B. B. McGlothlin

The introduction of new fracture propping agents that are brittle but much stronger than sand created the problem of what loading strength is required for a propping agent to be effective in a given formation. It is shown that the load at which the propping agent crushes should exceed the load at which total embedment in the fracture faces is possible. Simple laboratory tests to determine loading strength of the propping agent and embedment in the fracture faces, and use of these data in selecting a propping agent for a given formation, are discussed. INTRODUCTION One of the most important factors in the design of hydraulic fracturing treatments is the selection of a propping agent that can effectively provide the fracture flow capacity needed for stimulation of a well. Sand, once generally accepted as being synonymous with propping agent in hydraulic fracturing, is now recognized as having limited effectiveness in many formations because of its low resistance to crushing. Sand particles are brittle and have relatively low strength. Because of this property, sand particles are crushed in rocks that offer high resistance to the penetration of fracture faces by the proppant particles when the fracture attempts to close under the action of the overburden load. For rocks that offer a high resistance to penetration, deform able particles are more effective propping agents than sand. However, for this same type of rock, a propping agent that does not deform, yet does not crush, is often more effective. Thus, a rigid propping agent with sufficient strength to prevent crushing is desirable. A method for determining the strength required for a rigid propping agent to function effectively in given formations is discussed. BEHAVIOR OF RIGID PROPPANTS AND FRACTURE FACES RELATED STUDIES An early qualitative description of the reaction of propping sand in fractures was given by Hassebroek et al.' In discussing fracturing in deep wells, the authors mentioned that even though propping sand entered the fractures, a high flow capacity did not result due to crushing or embedding of the propping sand. Dehlinger et al.2 in discussing the reaction of propping sand surmised that, because of the hardness of sand particles, deformation occurred in the fracture faces contacting the propping sand. In later studies,3,4 methods of determining the embedment of propping sand in fracture faces of soft rock and the critical load at which propping sand is crushed by the fracture faces in hard rock were discussed. In working with de-formable proppants, Kern et al. considered proppant particles to be deformed into cylindrical disks by action of the overburden and then pressed slightly into the fracture faces by further action of the overburden. Rixie et al.'0 reported on embedment pressure and presented a method of selecting a propping agent for use in given formations. The propping agents included sand, walnut shells and aluminum pellets. All these studies have contributed materially to a better understanding of propping agent behavior; however, the strength of brittle proppants (sand, glass and ceramics) required to result in embedment rather than crushing has not been discussed. This topic will be covered in the ensuing discussion. PROPPANT PARTICLE CRUSHING—-EMBEDMENT For this discussion, a rigid propping agent is considered to be one that is brittle and fails under tensile stress when loaded to a critical value. In an earlier study4 it was shown that the Hertzian4 loading theory could be applied to a spherical brittle propping agent if the propping agent and fracture faces behaved elastically. At the failure of the proppant, the ratio of the load to the square of the diameter of the particle should be constant for a given material combination, or: Lc/dp2=C ............(1) A partial derivation of this equation from proppant and formation properties is included in the Appendix. Should a rigid particle not be crushed as a load is applied, it embeds in the fracture faces. A study3 of particle embedment in fracture surfaces has been published. The embedment can be described by an equation based on Meyer's metal penetration hardness relationships: d1/dp=B 1/2[L/dp2]m/2..........(2) In Eq. 2, B and m are constants that are characteristic of the rock; the significance of the other terms is shown in Fig. 1. A STANDARD DEFINITION FOR PROPPANT LOADING STRENGTH Eq. 1 is useful in appraising propping agent strength," but it is strictly applicable only when the area of contact between a particle and a fracture face (or loading plate)

Jan 1, 1967

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By L. H. Robinson

Triaxial compression tests have been performed to determine the strength characteristics of limestone, sand-stone and shale rocks subjected to controlled stress conditions. This control tuns exercised by varying the liquid pressures within and around a plastic-encased rock specimen. The pressure in the pores of the rock was varied throughout the range from atmospheric to 15,000 psig; the external pressure was changed over the same range with various positive pressure differences between is and the intertnal pressure. The data show that the rock strength increased and the mode of failure changed as the pressuire. surrounding the rock became greater than the pressure in the pores of the rock. These observations and the resu1ts of microbit drilling experiments indicate that the increased rock strength under pressure may bc an important effect in reducing drilling rare, but that other factors are probably of even greater importance. INTRODUCTION A large part of the research conductcd to reducc thc cost of drilling is directed toward improving present drilling technology and dcveloping new drilling methods. In spite of the fact that drilling is essentiaIly the act of making rocks fail, many details of the mechanism of failure are not known. It seems probable, therefore, that continuing studies of the fundamentals of rock failure can lay a foundation for future improvements in drilling technology. One of the factors which affects rock failure is the stress applied to the rock. This effect has been known for many years.'.'.; As an example, stress studics have been published by engineers' concerned with the strength characteristics of concrete in large dams. More recently, a number of investigators4-12 have explored the effects of stress on the strength of geologic formations and the geologic implications of their findings. During the last few years some research'" on rock strengths has also been conductcd in an attempt to gain additional insight into the factors which affeet rock drillability. In detcrmining the strength characteristics of rocks under different stress conditions, investigators have conventionally used triaxial compression equipment. wherein a jacketed rock cylinder is uniformly loaded from all directions and then compressed longitudinally. The results of this work have demonstrated that the mode of failure (brittle or malleable) is dependent upon the loading pressure, and that the strength of the rock increases as the loading pressure increases. These results clearly manifest that the stress, which is determined by the loading pressure, affects rock strength, and this implies that rocks under stress should be stronger and hence harder to drill. During the drilling of a porous rock the stress conditions are determined not only by the pressure surrounding the portion of the rock undergoing failure (confining pressure) but also by the pressure of the interstitial fluids within the rock (pore pressure). The importancc of both these pressures on the drilling rate of rocks has already been demonstrated by a number of investigators. Murray and Cunningham" found in microbit drilling expcriments that at constant pore pressures the drilling ratc decreased as the hydrostatic pressure surrounding an unjacketed, impermeable rock increased. Later Eckel" found that for jacketed Iimestone specimens the differcnce between hydrostatic (wellbore) pressure and formation (pore) pressure had an important effect on drilling rate. These observations of the effect of pressure on drilling rate emphasize that for drilling studies triaxial compression tests should be conducted under conditions of confining and pore pressure which simulate conditions underground. In the past, triaxial tests have been made under conditions which do not reproduce those underground. In particular, most of the tests on porous materials have keen made at varying confining pressures but with atmospheric pore pressures. In only one group of tests' was any data on the effect of pore pressurc reported, and these few data were on materials not representiltive of those encountered in drilling earth formations. The research described herein was initiated to deter-mine the importance of both internal pore pressure and confining pressure on failure characteristics of limestone. sandstone and shales. Triaxial loading equipment was used to obtain strength data at pressures up to 15,000 psig. An additional objective of this research was to apply these results to drilling rate studies by comparing them with the previously published drilling data of Murray and Cunningham" and of Eckel12. The work reported here is but one step in determining and evaluating the fundamental mechanisms which control drilling rate. Additional research is needed to clarify other aspects of the drilling process. The better

By B. H. Kear, B. J. Piearcey

The orientation and temperature dependence of the tensile and creep propevties oj Mav-M200 crystals halle been determined. Crystals oriented for single slip exhibit ,maximum ductility, minimum work hardening, and least creep resistance, whereas crystals in multiple slip orientations show nzinimu~n ductility, strongest work hardening, and greatest creep resistance. At 1400" and 1600°F there is a marked improzlenzent in creep strength for orientations approaching [001] and [111], indicating that interactions between dislocations gliding in intersecting octahedral slip systems play an important role in creep resistance. At 1800°F the creep strength is much less dependent on orientation, which is rationalized in terms of slip in cube planes as well as octahedral A frequent mode of failure in high-strength cast nickel-base superalloys is by intergranular fracture, particularly along those grain boundaries oriented transverse to the major stress axis. VerSnyder and ~uard' demonstrated that this problem could be overcome by eliminating transverse grain boundaries through unidirectional solidification. Piearcey and versnyder2 made use of this principle in the development of unidirectionally solidified gas turbine blades and vanes, where the growth direction of the columnar grain structure coincides with the axis of principal stress under operating conditions. The present investigation was undertaken to determine if further improvement in properties may be obtained by eliminating grain boundaries altogether, so as to take advantage of the well-known dependence of mechanical properties of single crystals upon the orientation. 1) EXPERIMENTAL PROCEDURE Single crystals of Mar-M200* were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold, and crystal growth was promoted from one end by appropriate gradient cooling. Tensile and creep specimens (2 in. diam by $ in. gage length) were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. The orientations of the specimens were determined by the Laue X-ray back-reflection method. Tensile tests were carried out in aWiedemann machine with furnace attachment, using a strain rate planes. In all orientations imzpvouement in the strength charactevistics of the material can be induced by heat treatment. Creep ad stress rupture data for (001) oriented crystals are compared with similar data obtailted previously joy random polycvystalline material, and also columnar grained material having a prejevved (001) orientation. The single-crystal )material exhibits both longer rupture life and lower minimum creep rate at all temperatuves, and the rupture elongation is comparable with that in the columnar grained material. From these results it is concluded that single crystals should and useful application in gas-turbine blades and tanes. The optimum orientation for a blade is considered to be with its axis of principal stvess parallel to (001) ou (111). of 0.0001 sec-'. Load and extension were recorded directly on an X-Y recorder. The strain measuring device consisted of extension arms attached to the grips at one end and leading out of the furnace to an LVDT (linear variable differential transformer) at the other. Creep tests were performed using a standard constant load creep frame. 2) DISCUSSION OF RESULTS 2.1) Structure of Alloy. The structure and segregation in as-cast and heat-treated Mar-M200 has been described in detail else where.~ The main features are as follows: the as-cast material is heavily cored, due to pronounced dendritic segregation during solidification; the dendrites are rich in tungsten and cobalt whereas the interdendritic regions are rich in chromium, titanium, nickel, and carbon. The structure consists of -60 vol pct coherent precipitate of y', basically Ni3(A1,Ti), in a matrix of y (nickel-base solid solution), interspersed in the interdendritic regions with minor MC carbides and -y' eutectic. The y' particles, and y-y' eutectic, contain more titanium, aluminum, and nickel, and less tungsten, cobalt, and chromium than the y matrix. Heat treatment partially removes segregation, eliminates the eutectic, refines the y' dispersion in y, and gives additional partially coherent M23Cs carbide. An as-cast crystal, therefore, is composed primarily of two oriented phases (y + y'), whereas the normally heat-treated crystal consists of three oriented phases (y + y' + MZ3Cs). Typical electron transmission micrographs of the y + y' structure are shown in Fig. 1. Crystals grown in the (100) orientation develop a simple unidirectional dendritic structure, Fig. 2, since (100) happens to be the preferred direction of growth for dendrites in this material. Crystals grown in the {110) and (111) orientations, however, tend to promote equal growth, generally in separate colonies, in the two and three geometrically favored (100) growth directions, respectively. In other orientations of growth, a single (100) dendrite direction generally pre-

Jan 1, 1968

By Lyman Johnson

Single crystals qf copper in "single slip" orientatiorzs have been deformed in compression. During defortnation all of the independent deformation parameters have been measured. These parameters consist of thefive strain components and three components descrihing the lattice rotation. By a finite strain analysis these pararmeters , forrming a deformation gradient martrix, are related to the amounts of slip on each of the twelve slip systems. The results show that the amount of secondary slip is about equal to the amount of primary slip. This is an order of magnitude larger than has been believed previoutsly. ACCORDING to early theory and experiments, when a single crystal of a fcc metal is deformed in tension or compression it should deform by slip on only one slip system until the stress axis reaches a symmetrical orientation.' However. the observation of a large increase in the secondary dislocation density during ..single slip" makes it clear that some slip does occur on secondary systems. Knowledge of the amount and distribution of this secondary slip is essential to a complete understanding of the mechanisms of single-crystal deformation. Ahlers and Haasen 2 and Mitchell and Thornton1 have tried to detect the amount of secondary slip in single crystals of silver and copper, respectively. Each simultaneously measured the angle A, between the tensile axis and the primary slip direction and the length 1 of a gage section of the specimen after incremental amounts of deformation in tension. The measured A, was then compared with the theoretical single slip angle hp. given by sin Ap = j sin . hO where ?o was the initial angle between the tensile axis and the primary slip direction and lo was the initial gage length. In both sets of experiments a small but systematic difference between ?e and ?p was found. This difference must be due to the occurrence of secondary slip. However, as Mitchell and Thornton1 pointed out. nothing quantitative can be said about the amount and distribution of this secondary slip from the measurements that they made. The reason that no quantitative conclusions could be made is because no unique solution for the distribution of slip on the twelve fcc slip systems can be determined from only two measured deformation parameters such as A and 1. There are, in fact, eight independent macroscopic deformation parameters that can be measured when a single crystal undergoes a homogeneous deformation. Physically these can be thought of as the five finite strain components and the three angles describing the crystal lattice rotation. All eight of these parameters were measured by Taylor4,5 for aluminum deformed in tension and compression. At that time the concern was to show that slip occurs on {111 (110) systems in fcc metals, and the mathematics were not available to determine what slip distributions were compatible with the measurements. In this paper the mathematics6,7 are developed that allow the slip distribution to be determined from these measurable macroscopic deformation parameters. The analysis is applied to the measurements of the strain and lattice rotation of copper single crystals deformed in compression. The results show that the amount of secondary slip is an order of magnitude larger than had previously been thought. CRYSTALLOGRAPHIC DESCRIPTION OF A HOMOGENEOUS DEFORMATION The deformation of a solid body can be represented by a transformation matrix F that transforms the un-deformed state into the deformed state. Consider a vector X connecting two material points in the unde-formed material and the vector x connecting the same two material points after deformation, where both vectors are referred to the same set of Cartesian axes. The final vector x is related to the initial vector X by the equation: X = FS. [2] Eq. [2] can be considered as the equation defining F, which is called the deformation gradient matrix. Its components are: If the deformation is homogeneous, the transformation is linear and the components of F are constants. Using subscript notation, if P is the unit vector in the initial direction of a material line, the components of the unit vector p in the direction of the same material line after deformation are given by:

Jan 1, 1970