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By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H'5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By F. Keller, R. H. Brown

BECAUSE of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1,2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. hot only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating I exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of *417S-T, 17S-T and 24S-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in z4S alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential dif-erence between the core and coating may be less than 0.16 volt, depending upon the thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24S-T, two are generally used; namely, the metallographic and the solution potential method.3 METALLOGRAPHIC METHODS Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24S-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By R. B. Hoy, Stanley J. LeFond, K. Reckling

Reported world production of natural diamonds approximates 40,000,000 carats a year (1980). The Republic of Zaire is the leading producer, with an output which is primarily industrial rather than gem grade. The USSR ranks second, the Republic of South Africa third, and Botswana, fourth. Diamonds are also mined in South-West Africa (Namibia), Angola, Ghana, Sierra Leone, and other African countries. In the western hemisphere, Brazil and Venezuela are the principal producers (Fig. 1). A very small output of diamonds is mined today it India, which was the first source of commercial production. In the US, efforts at commercial diamond mining have been confined to a small area near Murfreesboro, AR. The first diamond was found in a kimberlite pipe there in 1906. Small-scale trial mining has not, however, proved economical. Since diamonds were first discovered over 2,000 years ago, only about 260 tons have been mined. In order to obtain I g (5 carats) of diamonds, it is necessary to remove and process approximately 25 tons of rock. Recovering this small percentage involves a combination of highly developed techniques in mining, quarrying, and earth-moving, and extremely sophisticated recovery processes. End Uses Diamonds are used for two unrelated end uses; gem diamonds are jewels of great beauty while industrial diamonds are essential materials of modern industry. Although imitation stones are substituted for the gem diamond, none of these matches its properties sufficiently well to offer real competition. Synthetic industrial diamonds are now of a quality and size that permit them to be substituted for natural diamond in numerous industrial applications. For example, synthetic diamonds are available today in sizes up to 100 stones per carat (14/16 US mesh size). In addition, polycrystalline synthetic diamond inserts, such as De Beers Syndite®, General Electric's Compax® and Stratapax® and Megadiamond's Megapax® have replaced natural diamond in turning tools, mining and oil drilling bits and dressing tool applications. Gem Diamonds A diamond is a natural prism. It has the ability to bounce light rays (reflection), to bend them (refraction), and to break them into all colors of the rainbow (dispersion). This ability to modify light gives the diamond three characteristics for providing beauty. First is brilliance, the reflection of light back to the eye. Second is fire, dispersion of light into the colors of the spectrum. Third is scintillation, the "twinkling" that occurs when the diamond is moved (Bauer, 1969). The skill of the diamond cutter is required to unlock the brilliant, fiery beauty of a gem diamond (Fisher, 1966). Diamond-cutting skills have gradually developed over the centuries. The first cutters, in India, learned how to grind one rough diamond against another to remove their "skins" and to give them various shapes. This revealed some fire and beauty, but little compared to that of the diamonds that are cut today.

Jan 1, 1983

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

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 M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 0, i8, 19, 21, 22, 23. 24, 30. 34), concluded that a foundation for the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.1 One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur O. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 23 2,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. STADLER'S HYPOTHESIS WORTHLESS It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left-the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things, that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in fine crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1942

By J. B. Hess, R. L. Dietrich

In the mechanical twinning of magnesium on the {1012} planes the crystal-lographic deformation is such that, in the direction of the hexagonal axis [0001], twinning is possible only undef tension stress, while in the directions perpendicular to the hexagonal axis, twinning is possible only under applied compression. Thus in extruded magnesium and magnesium alloys where the extruded textures are best described as either [1010] or [1120] fibers,' the basal planes are all nearly parallel to the extrusion axis and such material is susceptible to ( 1or2 ) twinning by compression in the direction of the extrusion axis. In order to explain the results of cyclic stressing in alternate tension and compression upon the tangent elastic modulus in such material, Dorn and Thomsen2 have postulated that, following twinning under applied compression, a retwinning or un-twinning occurs as a result of residual microtensile stresses immediately upon removal of the applied compressive force. Recently, Carapella and Shaw4 have used this supposition of untwinning in magnesium in discussing their results on indentation hardness and on cold drawing of MI sheet. In trying to confirm this hypothesis by suitable direct experiments, the authors have been unsuccessful in detecting any evidence whatsoever that untwinning follows the release of applied compression and are forced to conclude that this hypothesis is improbable or, at least, that the quantity of material involved is small. For the experiments, small cylindrical specimens 0.040-in. diam. X 0.120- to 0.140-in. long were etched from 0.0625-in. extruded rod. The ends of the specimens were accurately faced off parallel in a jeweler's lathe. The compression jig was simply an ordinary set of micrometer calipers with an anvil interposed between the spindle and the specimen. The anvil was free to move axially but restrained from rotating so that the rotation of the spindle would not introduce a twisting stress on the specimen. With this arrangement the compressive strains could be estimated to 0.0001 in. and X ray pinhole photographs could be taken with or without load as required. Fig I is the pattern of an uncompressed specimen of AZ3I alloy, showing the approximate [1010] extrusion fiber. The X ray beam is normal to the extrusion axis; in this position it is particularly sensitive in detecting twinning if one directs his attention to the diffraction ring from the basal plane. Since twinning on (1072 planes produced an 86" reorientation of the crystal lattice, the original basal reflections occur at the 3 and 9 o'clock positions while the (0002) reflections from any twinned material will occur at the 6 and 12 o'clock positions. Fig 2 shows the same specimen compressed 3.0 pct, photographed while still under load. This strain has been just enough to produce a detectible amount of twinning and the sensitivity is roughly indicated by the fact that no alterations were produced in the intensities or maxima of the other diffraction rings. A strain of

Jan 1, 1949

By F. L. Kadey

The petrographic microscope is a well known tool in nonmetallic materials research. Its utility in the study of perlite is, therefore, not surprising. Valuable information has been derived on samples smaller than those needed by most other methods of analysis. Relatively little has been written about the petrographic analysis of perlite for two chief reasons: perlite is a material of relatively new commercial interest; and the independent prospector or expander, responsible for most studies, attacks the problem from an immediately practical viewpoint. Hence, petrographic studies of perlite have been limited to academic aspects. Rapid development of commercial interest in perlite has changed the situation. Mining and expanding companies now have effective research tools; and such instruments as the petrographic microscope have added materially to practical knowledge about this mineral. Petrographic techniques employed in the search for suitable deposits screen worthless samples rapidly and inexpensively compared with large-scale expanding tests. Hence, only samples of potential quality are selected for further testing. Field appearance of perlite reveals little about its true identity and practically nothing about its commercial significance. Consequently, any method that can be used to separate the "wheat from the chaff" is valuable. In addition to the conventional thin-section and immersion methods used in evaluation of crude perlite, petrographic microscope techniques have contributed to the study of expanded perlite. When apparently similar materials behave as differently in use as perlites, the internal structure of the individual particles becomes a subject of great interest. The purpose of this paper is to discuss some of the petrographic techniques used to characterize this material. WHAT IS PERLITE AND WHERE IS IT FOUND? Perlite was at first described as a glassy rhyolite possessing a pearl-like luster and exhibiting numerous concentric cracks resembling an onion skin appearance.' Fig. 1 is an illustration of perlite in this classical sense. Recently, its definition has taken on a commercial connotation: an acid volcanic containing 2 to 5% of combined water that, when heated rapidly to the softening point of the glass, coincident with the volatilization of the combined water, expands or "pops". Fig. 2, although hardly fitting the classical description given by Johannsen, is an excellent perlite in the commercial sense. It may occur as a breccia in rhyolite, (Fig. 3) and sometimes it is associated with obsidian nodules, as illustrated in Fig. 4. The term perlite includes the expanded product also. In the United States, perlitic rocks are restricted to the western part of the country. 2 Elsewhere in the northern hemisphere, European occurrences follow a belt beginning in Iceland and extending in a southeasterly direction through Scotland, County Antrim in Northern Ireland, and through the Massif Central of France, Germany, and Hungary; thence, into Italy and Sardinia, and through some of the Aegean Islands. A general oriental belt extends from Japan through Australia and New Zealand. Rhyolitic areas elsewhere in the world undoubtedly contain perlite.

Jan 1, 1963

By Richard M. Foose

Five miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. Geology Lower Cambrian Antietam quartzite and the Rilontalto quartzite, stratigraphi-cally older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65" to vertical. The clay crops out at an elevation of about 1000 feet. Origin and Character The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there Are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about loo ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: SiO2, 67.05 per cent; Al2O3, 22.27; Fe2O3, 0.40; CaO, 0.00; TiO2, 1.05; MgO, 0.52; Na20, 0.04; K2O, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1948

By Richard M. Foose

Five miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. Geology Lower Cambrian Antietam quartzite and the Rilontalto quartzite, stratigraphi-cally older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65" to vertical. The clay crops out at an elevation of about 1000 feet. Origin and Character The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there Are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about loo ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: SiO2, 67.05 per cent; Al2O3, 22.27; Fe2O3, 0.40; CaO, 0.00; TiO2, 1.05; MgO, 0.52; Na20, 0.04; K2O, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1948

By Donald W. Scott, L. A. Roe, B. J. Sweo

INTRODUCTION THIS paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizers and organic dyes, and 35 parts of water are added to loo parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder' in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the overspray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1947

By J. B. Macelwane

Geophysics differs from geology and physics in in many respects. In the first place, geophysics is a complex science embracing the fields of seismology, geomagnetism, geoelectricity, geodesy, meteorology, vol-canology, physical oceanography, physical hydrology, tectonophysics and exploration geophysics. Geology is also a complex science and so extensive in its various fields that no one can master them all, and no part of geology deals in any sense with several of these fields of geophysics. In the second place, geophysics makes use of methods and instruments that are derived primarily from the science of physics. Geology, on the other hand, has methods of its own and it draws its borrowed techniques and its instrumental equipment not only from physics but also and perhaps primarily from chemistry and biology. The difference, therefore, between the geophysicist and the geologist lies partly in the phenomena that are observed, partly in the methods and instruments with which each carries on his exploration; but partly also, and perhaps principally, in the habitual attitude of mind and in the background of specialized training with which each approaches the problems presented by this planet of ours. The geologist as such, therefore, is no geophysicist. On the other hand, the physicist is not a geophysicist either. Isolation of each problem in a closed laboratow system under complete control is fundamental to the methods of the physicist. The geophysicist must apply physical instruments and physicomathematical reasoning to the study of physical quantities in their undisturbed natural environment. What, then, is a geophysicist? In the sense that he is a trained expert in all of the geophysical sciences, I do not believe that such a person ever existed. It would be beyond the possibilities of a single lifetime. I think there is confusion in our ideas and in our use of terms. We are not all thinking of the same thing when we say geophysics or geophysicist; yet we seem to talk as though we were. It is as absurd to say that the whole of geophysics belongs to geology because the field of a particular type of geophysicist—the exploration geophysicist —calls for some knowledge of geology as it would be to say that the whole of biology belongs to geology because a particular type of biologist—the paleontologist— needs some knowledge of geology. Development of a Geophysicist Since it is impossible to become an expert in all the fields of geophysics, and since students entering college seldom know the field they will choose as a career, what would we suggest as the best general preparation for work in geophysics, whether as a meteorologist, an oceanographer, a seismologist, a geodesist, a geomagneticist, a volcanologist, a tectonophysicist, a hydro1 ogist, or an exploration geophysicistp we may distinguish five phases in the development of a geophysicist: (I) his mathematical and scientific studies in high school; (2) the general mathematical and scientific

Jan 1, 1946

By I. Hawke, K. Barron

I. Hawkes (Postgraduate School in Mining, University of Sheffield, Sheffield, England) — The photoelastic stressmeter is proving to be a very practical tool for 'in-situ' measurements in the fields of civil and mining engineering and Barron's article has therefore come at a very opportune time, supplementing as it does, the considerable amount of laboratory and field data which is being accumulated.1,2,3 There are however several points relating the application of Barron's conclusions to the practical use of the meter which require further elucidation. EASE OF READING If the photoelastic stressmeter is to have a wide application, the fringe orders must be easily measured. The system adopted by the writer and his colleagues at Sheffield for the uniaxial stress case is to read the fringe order at the 45 point, 0.20 in. from the center (11/4 in. diam meter). This procedure has been recommended because the fringes not at this point form a very distinct 'eye' which is obvious even to those who have had little experience with photoelastic fringe patterns. Barron points out that this point can also be used up to a stress ratio of 0.33 and in practice this is normally done. In biaxial fields above a ratio of 0.33 the 'eye' is no longer apparent and the fringe order must be ascertained at some other point. The writer and his colleagues experimented at various points and finally chose a point at a distance 0.175 in. (11/4 in. diam meter) on the minor stress axis and fixed this point on the meter by inserting a collar of this diameter. This procedure enables the 'eye' technique to be used for uniaxial stresses as the 'eye' falls outside the collar; any other technique for biaxial patterns would require lines to be engraved on the meter itself and reading difficulties would be experienced by all but the most highly trained. It is interesting to point out that in a great many field applications ranging from underground pillars to building foundation piles the stresses measured have been uniaxial. In such cases, reading the fringe order has been simple even for unskilled persons. SENSITIVITY The photoelastic stressmeter acts as an inclusion, and as such its theoretical behavior is as described by Barron's mathematical analysis. When considering its practical application, however, it must be remembered that rocks and concrete are not mathematically ideal substances. The theory relates the fringe order in the meter to the stresses and the E (Young's Modulus) and the µ (Poisson's Ratio) values of the surrounding material. There is of course no unique E or µ value for rocks or concrete. These values change both with stress level and time load application sometimes to the order of 300%. We at Sheffield have very accurately calibrated the photoelastic stressmeter in a wide range of materials and have also measured the average E values for these materials. The results prove that the meter sensitivity

Jan 1, 1965

By J. B. Macelwane

Geophysics differs from geology and physics in in many respects. In the first place, geophysics is a complex science embracing the fields of seismology, geomagnetism, geoelectricity, geodesy, meteorology, vol-canology, physical oceanography, physical hydrology, tectonophysics and exploration geophysics. Geology is also a complex science and so extensive in its various fields that no one can master them all, and no part of geology deals in any sense with several of these fields of geophysics. In the second place, geophysics makes use of methods and instruments that are derived primarily from the science of physics. Geology, on the other hand, has methods of its own and it draws its borrowed techniques and its instrumental equipment not only from physics but also and perhaps primarily from chemistry and biology. The difference, therefore, between the geophysicist and the geologist lies partly in the phenomena that are observed, partly in the methods and instruments with which each carries on his exploration; but partly also, and perhaps principally, in the habitual attitude of mind and in the background of specialized training with which each approaches the problems presented by this planet of ours. The geologist as such, therefore, is no geophysicist. On the other hand, the physicist is not a geophysicist either. Isolation of each problem in a closed laboratow system under complete control is fundamental to the methods of the physicist. The geophysicist must apply physical instruments and physicomathematical reasoning to the study of physical quantities in their undisturbed natural environment. What, then, is a geophysicist? In the sense that he is a trained expert in all of the geophysical sciences, I do not believe that such a person ever existed. It would be beyond the possibilities of a single lifetime. I think there is confusion in our ideas and in our use of terms. We are not all thinking of the same thing when we say geophysics or geophysicist; yet we seem to talk as though we were. It is as absurd to say that the whole of geophysics belongs to geology because the field of a particular type of geophysicist—the exploration geophysicist —calls for some knowledge of geology as it would be to say that the whole of biology belongs to geology because a particular type of biologist—the paleontologist— needs some knowledge of geology. Development of a Geophysicist Since it is impossible to become an expert in all the fields of geophysics, and since students entering college seldom know the field they will choose as a career, what would we suggest as the best general preparation for work in geophysics, whether as a meteorologist, an oceanographer, a seismologist, a geodesist, a geomagneticist, a volcanologist, a tectonophysicist, a hydro1 ogist, or an exploration geophysicistp we may distinguish five phases in the development of a geophysicist: (I) his mathematical and scientific studies in high school; (2) the general mathematical and scientific

Jan 1, 1946