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By R. N. Hoffman

A new technique for determining capillary pressure curves has been developed and tested. The technique differs from previously reported centrifuge techniques in that the centrifuge is slowly accelerated from zero to the maximum desired speed rather than being held constant at particular, progressively higher speeds. An important advantage of this technique over other methods of determining capillary pressure curves is the short time required to obtain the desired amount of data over the chosen pressure range. For example, to obtain 30 data points between 1.2 and 104 psig with a 1.55-in. long, 3/4-in. diameter core using a brine-air system, 6.6 hours were required with this technique. An equally important development of this paper is an analytic method for the conversion of the data from the centrifuge experiment to capillary pressure curve data. Previously there has been only an approximate conversion available. Although the capillary pressure curves determined by this technique appear to be as accurate as those determined by other techniques, the accuracy could be improved if certain variables, not treated in this experiment, were investigated. Among these are the dynamic distortion of the centrifuge equipment and imperfect initial saturation of the cores. INTRODUCTION Pirson 1 defines capillary pressure in a porous medium as "the differential pressure that exists between two fluid phases at their interfaces when they are distributed under static equilibrium within a porous material". Capillary pressure in rocks is known to be a function of fluid saturation, among other things, and a capillary pressure curve is defined for the purposes of this paper as a plot of the capillary pressure-wetting phase saturation relationship for a particular rock sample. Several methods are used for determining capillary pressure curves for small rock cores. Prominent among these are the semi-permeable barrier, mercury injection, and, to a lesser extent, centrifuge methods. The semi-permeable barrier method is currently the most popular. It features simplicity in both execution and the mathematical conversion of the experimental data into a capillary pressure curve. The main disadvantages of the semi-permeable barrier method are the time required — as long as two months — to obtain several points for the curve, and a fairly low maximum pressure before breakthrough of the non-wetting phase into the barrier occurs, for example, about 32 psig for a brine-air system. It is for these reasons that other methods such as the centrifuge method have been introduced. High accelerations and the absence of a barrier result in quicker attainment of saturation equilibrium at a given pressure. However, the centrifuge method involves much more expensive equipment and more difficult procedures and calculations than does the barrier method. The purpose of this investigation has been to improve the equipment and procedures of the centrifuge method and to develop an analytic method for the conversion of the experimental data into a capillary pressure curve. Hassler and Brunner did the original work in the determination of capillary pressure using a centrifuge. In their work the centrifuge speed was increased in a step-wise manner, each speed being held constant until saturation equilibrium was reached in each core. Saturation equilibrium was indicated when the volume of liquid collected in the graduated pipette of the core holder remained constant. According to Hassler and Brunner, equilibrium was reached in "a few minutes to one-half hour or more". In the centrifuge method, as opposed to the barrier method, the fluid saturation of the core is not a constant throughout the length of the core, but varies with the radius of centrifugation. Also, the capillary pressure cannot be read directly but must be calculated from a knowledge of the centrifuge speed and other parameters. For these calculations, Hassler and Brunner derived the following equations:

By Sidney A. Swensrud

The 24-in. crude-oil line. and- the 20-in. petroleum-products line, built as a war emergency by the United States Government and running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue nor-inal ocean tanker movements from the Gulf Coast to the East Coast. The postwar disposition of these lines may be considered as one of the important problems of the postwar readjustments in the oil industry, if not the most important one. In the first place there appear to be many complications in keeping the lines in crude-oil or petroleum-products service. This conclusion was reached also in a study by T. E. Swigart, President of Shell Pipeline Corporation.' Since the lines are too largc for any one company to utilize, and since it appears likely that a surplus rather than a deficiency of tankers will exist after the war, most companies probably will feel that they can achieve lower costs and more satisfactoiy results from the resumption of tanker movements to the East Coast rather than by endeavoring to take over or utilize the capacity in the large pipe lines under some tariff-rate structure. As for using the lines for making deliveries to the middle west or central eastern areas, it would appear that when the war is over and normal transportation arrangements can be resumed, there will be no need of any extra capacity for such deliveries. Therefore, the War Emergency lines could be utilized for this purpose only if privately owned pipe lines and other transportation facilities were to be displaced. Against this rather unprepossessing prospect for use in petroleum or product service is the fact that at or near the source of the lines lie the greatest developed gas reserves in the world, for much of which there is at present no satisfactory market outlet; and at the other end of the lines lies one of the greatest concentrations of population in the world, which is not now served by natural gas. These who have been fortunate enough to use natural gas can have little doubt of its desirability as a domestic fuel. An analysis of the market potentialities and comparison with other areas where natural gas is being distributed, and where it has displaced manufactured gas, makes it seem clear beyond question that the full capacity of both of the large-diameter lines could be fully utilized in this service, and this without creating any undue drain upon the gas reserves of the nation. On the basis of an estimated capacity of roo to 120 billion cubic feet per year, the gas that might be marketed through these lines would amount to only 3 to 4 per cent of the total con-

Jan 1, 1944

By Sidney A. Swensrud

The 24-in. crude-oil line. and- the 20-in. petroleum-products line, built as a war emergency by the United States Government and running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue nor-inal ocean tanker movements from the Gulf Coast to the East Coast. The postwar disposition of these lines may be considered as one of the important problems of the postwar readjustments in the oil industry, if not the most important one. In the first place there appear to be many complications in keeping the lines in crude-oil or petroleum-products service. This conclusion was reached also in a study by T. E. Swigart, President of Shell Pipeline Corporation.' Since the lines are too largc for any one company to utilize, and since it appears likely that a surplus rather than a deficiency of tankers will exist after the war, most companies probably will feel that they can achieve lower costs and more satisfactoiy results from the resumption of tanker movements to the East Coast rather than by endeavoring to take over or utilize the capacity in the large pipe lines under some tariff-rate structure. As for using the lines for making deliveries to the middle west or central eastern areas, it would appear that when the war is over and normal transportation arrangements can be resumed, there will be no need of any extra capacity for such deliveries. Therefore, the War Emergency lines could be utilized for this purpose only if privately owned pipe lines and other transportation facilities were to be displaced. Against this rather unprepossessing prospect for use in petroleum or product service is the fact that at or near the source of the lines lie the greatest developed gas reserves in the world, for much of which there is at present no satisfactory market outlet; and at the other end of the lines lies one of the greatest concentrations of population in the world, which is not now served by natural gas. These who have been fortunate enough to use natural gas can have little doubt of its desirability as a domestic fuel. An analysis of the market potentialities and comparison with other areas where natural gas is being distributed, and where it has displaced manufactured gas, makes it seem clear beyond question that the full capacity of both of the large-diameter lines could be fully utilized in this service, and this without creating any undue drain upon the gas reserves of the nation. On the basis of an estimated capacity of roo to 120 billion cubic feet per year, the gas that might be marketed through these lines would amount to only 3 to 4 per cent of the total con-

Jan 1, 1944

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Jan 1, 1929

By Freeman Bishop

This year the metal mining industry is in for some difficult decisions as the nation struggles to control inflationary pressures resulting from higher production costs and a money-squeeze policy. Re- clouding these problems will be campaign oratory as Congress seeks reelection. Charges will be hurled back and forth between a Republican White House and a Democratic Congress. Inflation and Vietnam will be the big one. Hut pollution i. coming on strong. President Nixon has formed a new Council on Environmental Quality although he already had named a similar unit within his Cabinet six months ago. Both are charged with bringing 1.0 bear all of the Federal Government's talents on the focal points of antipollution measures The biggest task will be to find out how many different "units" are currently mixed up in these efforts.

Jan 1, 1970

By M. D. Hassiaslis

THE nature of a collector-coated mineral surface has been the subject of some experimentation and much speculation. Various aspects of the problem have been isolated and studied; it is probable, however, that there exist aspects as yet unrecognized, which are needed for a complete description of the system. The recognized elements of the problem are: 1-The nature of the chemical units comprising the film and the nature of the forces holding these chemical units to the mineral surface; 2-The orientation of the chemical units at the surface; and 3-The disposition of the collector units at the mineral surface. This report touches upon all three aspects of the broad problem; it deals, however, with a new and heretofore unrecognized element-the mobility of the collector units in the two dimensions of the solid-liquid interface.

Jan 11, 1951

By Charles R. Keyes

In the dry regions of the globe many silver-deposits display certain remarkable features, which at the same time are so totally unlike anything met with among ore-bodies elsewhere that they hare long presented exceptional dificulties, not only to a satisfactory explanation of their origin, but to economical milling. A most striking peculiarity of these ores is the haloid character of many of their bonanzas. To this fact more than to any other may be ascribed most of the unusual uncertainties of mining-operations in desert countries—the marvelous local richness of the ores under certain conditions and the often abrupt transition to utter poverty; the inadequacy of ordinary prospecting customs and the constant devising of new exploratory methods; the unaccountable losses in smelting and the continual change in treatment-practice. For these anomalies certain climatic conditions seem to be chiefly responsible.

Jan 1, 1912

By C. H. Ma, J. S. Makris

This paper describes a modified X-ray diffraction microscope wzethod based on the general principles of Berg-Bawett's Method, Lang's Method, and Woosters1 Technique. This new method may be used for stationary or oscillatory photomacrographs, with both reflection and transmission techniques. In the stationary technique, a small point-source of a divergent X-ray beam of white radiation is used; in the oscillatory technique, a monochromatic divergent beam is employed. The chief advantages of the method described herein are that only approximate alignment of the Bragg angle -of-interest is needed during exposure, and that a large portion of a crystal-specimen surface can he irradiated. In recent years, the study of dislocations through X-ray diffraction microscope techniques has received considerable attention as concerns the per,fection of single crystals. Very promising results have appeared in the literature.'-' These techniques are very useful when the dislocation density of a crystal is near 105 per sq cm or lower. The principle of X-ray diffraction microscopy is based on the differential effect of X-ray primary extinction between the distorted parts and the perfect parts of a crystal. When an X-ray beam impinges on a set of planes of a crystal at the correct Bragg angle, diffraction of X-rays will occur with a 90-deg phase shift of the diffracted beam. This once-diffracted beam still forms the correct Bragg angle with the planes ahead of it, if the planes are not distorted. Thus, part of the strength of the once-diffracted beam is rediffracted and the beam continues to travel in the direction of the primary X-ray beam. This twice-diffracted beam not only takes away part of the strength of the once-diffracted beam, but also causes destructive interference with the primary beam because it now is exactly 180 deg out of phase with the primary beam. As the primary beam goes farther and farther into the crystal, its intensity is continuously weakened. Asa result, the ultimate X-ray diffraction power of a set of undistorted planes is largely extinguished. This phenomenon is called primary extinction.1,2'4 If the set of planes ahead of it is distorted, the once-diffracted beam will have less chance to be rediffracted, because it could not meet the exactly correct Bragg angle for rediffraction. If a part of the beam does rediffract, this twice-diffracted beam is not exactly 180 deg out of phase with the primary beam, and thus it causes less destructive interference. As a result, the registered X-ray diffraction power of the distorted part of a crystal appears stronger than that of the perfect part. Thus, point-by-point contrast of a diffraction image is theoretically possible from a crystal containing dislocations. Two most popular X-ray diffraction microscope techniques today are Berg-Barrett's Method and Lang's Method. Both of these techniques require a

Jan 1, 1964

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably her product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too he, since finer particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely fine kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater dificulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1947

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably her product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too he, since finer particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely fine kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater dificulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1947

By Sultan Amerie

PERSIA looms up more prominently each year as one of the richest oilfields in the world. The actual production in the south and the possibilities in both the north and the south are very great. The output in the south, where the Anglo-Persian Oil Co. operates a wide concession, is steadily increasing, the returns for the fiscal year 1922-23 being 2,957,028 tons. The estimated production for. 1923-24 is 3,775,000 tons. The figures for the past few years have been as follows: 1918-19 1,106,415 tons 1920-21 1,743,557 tons 1919-20 1,385,301 tons 1921-22 2,327,221 tons According to the company's last annual report, the production from the -Persian fields operated by its subsidiaries has been well maintained and is now being increased to deal with the expanding off-take of the company's refineries at Abadan, Persia, and Dandarcy, Wales. Test drilling in an entirely different area in Persia indicates the existence of a new oilfield, which it is intended for the time being to hold as a reserve.

Jan 3, 1924

Inflation, tight money and keen competition spur companies to consider advanced material handling systems capable of reducing cost per ton of moving ore, waste or men and supplies. Since transportation charges account for an average of about 25% of the total delivered price of a product, then this cost center may actually determine the economic value of a new deposit. This being so, it is interesting to note that of the 1.4 billion tons of revenue freight carried by all Class I carriers of the nation in 1967, over 247 million tons or 17.5% were industrial minerals or products dependent on industrial minerals, i.e., glass, gypsum board, brick, etc. Because most bulk commodities have a comparatively low market value and are usually classified for lower than normal freight rates, railroads rely on large volumes and better equipment utilization to effect an equitable return. It is for this reason that the unit and shuttle train concept came into being. The average rate per ton-mile of all materials hauled by rail in 1968 was 1.31 cents. The low rates existing for industrial minerals contributed to this low average as did unit and shuttle train rates.

Jan 10, 1969

The resin-in-pulp (RIP) ion exchange process was originally conceived by the Atomic Energy Commission in the early 1950's. However it was developed to commercial success by the Anaconda Co. at its 3000-tpd ore processing mill in Grants, N. M. Essentially, the Anaconda mill's crushing, grinding and acid leaching operations are the same as at the nearby Kerr-McGee mill, except that Anaconda uses manganese dioxide instead of sodium chlorate as oxidant during acid leaching. The real differences between the two mills become evident when considering how Anaconda treats its leached materials.

Jan 8, 1974

By H. J. Morel-Seytoux

Methods of predicting the influence of pattern geometry and mobility ratio on water flooding recovery predictions are discussed. Two methods of calculation are used separately or concurrently. The analytical method yields exact solutions in a convenient form for a unit mobility ratio piston-like displacement. A few typical pressure distributions, sweep efficiencies and oil recoveries are presented for various patterns. For non-unit mobility ratio, one may resort to a numerical method, such as that of Sheldon and Douherty. 1,2 Because the domains of applicability of the analytical and numerical techniques overlap, the exact solutions provide estimates of the errors in the numerical procedures. The advantages of the analytical and numerical methods can be combined. To develop a numerical technique as independent of geometry as possible, the physical space is transformed into a standard rectangle. The entire effect of geometry is rendered through one term, the "scale-factor", derived from mapping relations. The scale factor can be calcu-lated from the exact unit-mobility ratio solution for the particular pattern of interest. By this means recovery performances for arbitrary mobility ratio con be obtained for many patterns. A sample of tesults obtained in this manner is presented. INTRODUCTION Pattern geometry and mobility ratio are two major factors in making a waterflood recovery prediction. Because assisted recovery has become increasingly important to the oil industry, pattern configuration and mobility ratio also assume a greater significance in the assessment of the economic value of recovery projects. The influence of pattern geometry and mobility ratio in shaping a recovery curve and on the other quantities of interest to the reservoir engineer is the main subject of this paper. Much effort has already been spent on estimating quantitatively the influence of either pattern or mobility ratio or both on oil recovery. The literature reports many investigations of this nature. 3-9 However, many results or methods of recovery prediction presented in the literature cannot be considered fully satisfactory. Even for unit mobility ratio and piston-like displacement, where analytical solutions are available, the literature shows discrepancies. For non-unit mobility ratio, the divergence in the results is extreme. For infinite mobility ratio in a repeated five-spot, depending on the investigator, the sweep efficiency ranges from 0 per cent to 60 per cent. With respect to the influence of pattern on recovery, only the repeated five-spot has received much attention. Other confined patterns and pilot configurations have received very little attention. Two calculation methods are presented in this paper, either separately or concurrently: the analytical method of potential theory and the numerical method of finite-difference approximation. The analytical method is more restricted in scope than the finite-difference method, but it has the definite advantage of providing exact solutions within its range of applicability. If a unit-mobility ratio piston-like displacement is assumed, the analytical approach is possible. A few typical results are reported in this paper; the detailed description of the general method and of a great variety of results will be the subject of other articles. Fornon-unity mobility ratio, we must resort to a numerical scheme. The numerical technique is that which was described by Sheldon and Dougherty.l,2 It is not limited to piston-like displacement. However, mainly single interface results will be presented here. Because the respective domains of applicability of the analytical and the numerical method overlap, useful comparisons of exact and numerical solutions can be made for a variety of patterns. The advantages of the analytical and numerical approaches can be combined. The reason for the success of this analytical-numerical approach can be summarized in the following two points: 1. The numerical solution for arbitrary mobility ratio can be programmed most efficiently when the physical space in which the displacement actually takes place is transformed into a standard shape; and 2. This can be done with remarkable simplicity whenever an analytical expression for the pressure

Jan 1, 1966

By E. L. Dougherty

A phenomenological theory for a one-dimensional unstable miscible displacement similar in type to the Buckley-Leverett model but including the effects of mixing is proposed An equation giving the fractional flow of pure solvent through an oil phase containing dissolved solvent is derived including the effects of gravity and nonbomogeneities. Numer ical integration of the resulting pair of nonlinear hyperbolic partial differential equations gives volumes of dissolved and undissolved solvent as functions of space and time. Parameters in the model which characterize mixing due to dispersion were determined from experimental data; the parmeters correlated with viscosity ratio. The results indicate that the rate of dispersive mixing is proportional to volumetric flow rate Incorporated into our equations were Koval's heterogeneity factor H. which characterizes mixing due to channeling. This allowed satisfactory predictions of displacement behavior observed in horizontal floods in nonhomo-geneous cores; but in most cases the values of H which we used were considerably larger than those used by Koval. INTRODUCTION It has been shownl,2,3 that for favorable viscosity ratios, the diffusion equation with convection satisfactorily describes the behavior of a miscible displacement in a porous media. Numerous attempts to develop a satisfactory mathematical description for the case of unfavorable viscosity ratio have been reported, but they have met with only partial success. These attempts, which are reviewed by oval! have taken two approaches: (1) development of a flow model akin to the Buckley-Leverett approach for immiscible displacement neglecting the effects of mixing5,6 and (2) simultaneous application of Darcy's Law for flow and the diffusion equation with a convection term for mass transfer.7,8,9 We set out to construct a mathematical model of Type 1 including, though, the effects of mixing. Based upon a set of hypotheses, we derived a pair of nonlinear hyperbolic partial differential equations which describe in a one-dimensional system the combined effects of flow and mixing. To work with these equations it was necessary to develop a fractional flow formula. The combined system was integrated numerically using the method of characteristics. In our equations the mixing process is characterized by four parameters. Three of these, labeled ß, P1 and P2, account for dispersive type mixing. The fourth is the heterogeneity factor H, proposed by Koval to account for channeling due to nonhomogeneities in the porous media. Values of the parameters which would cause agreement between theory and experiment were determined by trial-and-error for miscible floods conducted in horizontal cores of both homogeneous and heterogeneous materials. Calculations were also performed for vertical floods in homogeneous cores. The purpose of this paper is (1) to present the details of the mathematical analysis, (2) to present the results of the calculations, (3) to consider what light the results shed on the mixing process in an unstable miscible displacement, and (4) to provide a firmer foundation for the correlation technique developed by Koval for predicting the behavior of unstable miscible floods. STATEMENT OF PROBLEM The problem is to construct a mathematical model which describes in one dimension the observed behavior in an unstable miscible displacement. The approach is phenomenological in that the equations are based on assumptions which violate certain physical precepts known to apply to the displacement phenomenon. However, the assumptions do allow us to account mathematically for the more essential phenomena. The work is of value if we can quantitatively predict experimental results which heretofore could not be predicted, even though the synthetic nature of the model belies complete explanation of the observations. We assume that the system is comprised of two contiguous flowing phases. One phase, which we call free solvent, has the properties of pure solvent. We call the fraction of the pore volume occupied by this phase the solvent saturation, designated s. The oil phase consists of oil containing dissolved

By A. L. Lee, M. H. Gonzalez, R. F. Bukacek

Experimental viscosity data for methane are presented for temperatures from 100 to 340F and pressures from 200 to 8,000 psia. A summary is given of the available data for methane, and a comparison is presented for that data common to the experimental range reported in this paper. Correlation of the data is presented, and predicted values are given for temperatures up to 460F and pressures up to 10,000 psia. INTRODUCTION The increasing ranges of temperature and pressure at which fluids are produced, transferred and processed in the petroleum and chemical industries stress the need for accurate information on physical properties, both for engineering calculation and for improving the methods used to estimate physical properties. A survey of the literature reveals that disagreements between published data on the viscosity of methane are common and that most investigations have been conducted over restricted temperature and pressure ranges. This situation made it desirable to undertake an investigation with a scope common to most of the literature data available. APPARATUS AND MATERIALS The apparatus used in this investigation was the capillary tube viscometer'described by Dolan,10 with modifications introduced in the general design and operation of the instrument. It has an effective pressure range from 14.7 to 10,000 psia and a temperature range from room temperature to 400F. The design of the viscometer is based on the establishment of a manometric head between two vessels containing the test fluid and a volume of mercury. The reservoirs are connected by a capillary tube through which the test fluid flows and a tube through which mercury flows. A pressure gradient is established by elevating one of the vessels above the other, the resulting flow of mercury displacing the test fluid through the capillary. The schematic diagram of the system (Fig. 1) shows the arrangement of the equipment auxiliary to the viscometer. The density cells assembly (E, Fig. 1) was not used in this investigation since reliable data are available on methane. 23 The assembly consists of a bank of eight 316 stainless steel pycnometers. Experimental values of the density of a natural gas19 and i-butane14 samples have been obtained for pressures up to 8,000 psia and temperatures up to 340F. The methane used was obtained from the Southern California Gas Co. Mass spectrometric analysis showed a composition of 99.8 percent CH4, 0.1 percent C2H6 and 0.1 percent C3H8. EXPERIMENTAL VALUES AND ACCURACY OF DATA Determinations were carried out at several temperatures. With the temperature in the cabinet controlled at a given level, a series of runs were made at various pressures. To establish pressures lower than that obtained from the methane cylinder, it was necessary to vent the gas slowly to the atmosphere until the desired pressure was reached. The consistency of the test run time for a particular condition can be used as a criterion for the accuracy of the data. A further check is obtained by comparison of the viscosity values obtained using different driving heads. To establish the instrument's reproducibility, a large number of runs were made at three completely different conditions of temperature and pressure. Data obtained were analyzed statistically to determine the most reliable value for the variance of the experimental data. It was found that the variances of the data taken at different experimental conditions were not statistically equivalent, but they were small. The largest variance was found at 8,000 psia and 100F, where the standard deviation was 0.385 micropoise. Therefore, 99.9 percent of the data can be expected to fall within 1.15 micropoises of the population mean, except for the intervention of systematic errors in operation.

By Eugene F. Broome, Hugh A. Walls

Self-diffusion coefficients were measured using the modified shear cell technique over a temperature range from 31" to 401°C. These data agree within experimental error with those of Petit and Nachtrieb, which were determined from 30°to 99°C. LIQUID self-diffusion behavior in gallium has been studied previously by Petit and Nachtrieb&apos; using their shear cell technique.&apos; Data were obtained in that investigation over temperatures ranging from 30.6 to 98.7"C, and these comprise the only published data for liquid gallium. In the work reported here, diffusion data were obtained from 30.8 to 400-9.Cusing a shear cell technique different from that of Petit and Nachtrieb. This modified shear cell method and the mathematical analysis for diffusion in a finite capillary geometry have been previously described.3 PROCEDURES AND ANALYSIS The segments of the modified shear cell were fabricated from types 304 and 316 stainless steel. No corrosion problems with gallium were encountered until attempts were made to obtain data at 500°C. The diffusion capillary diameter was 1.59 mm and capillary lengths for the four sets of cell segments used are given in Table I. Gallium with a purity of 99.999 wt pct was obtained from Var-Lac-Oid Chemical Co. The gallium-72 isotope used to measure the self-diffusion coefficients was produced from this inert gallium by irradiation in The University of Texas Reactor Facility, and was checked for radiochemical purity. Following a period of isothermal diffusion controlled to within 0.0l°C, the contents of each capillary section were emptied into a counting planchet, weighed to assure that gallium had not been lost during handling, and the radioactivity determined by windowless gas-flow proportional counting. Great care was taken to obtain a reproducible counting geometry for the samples. Diffusion coefficients were obtained from the solu-tion3 to the diffusion equation for the modified shear cell problem, viz.: in which B2= C2(t)Li + L2)- CSL1-COL2 P* (C0-Cs)(L1+ L2) and L, and L2 are the capillary segment lengths. The step-function initial concentration distribution was expressed as C(x,O) = C, for -L1 = x < 0 and C(x,O) = Co for 0 < x 5 L?. Also, C2(0 = ^- fcix,t)dx Computation of the diffusion coefficients was done numerically as described in our earlier paper.3 Because of the short half-life of gallium-72 (14.1 hr) and the relatively long counting times taken to give a precise value of the diffusion coefficient, it was necessary to account for the radioactive decay both during the actual count and between counts for different samples (before and after diffusion). Thus, the average count rate Cz(t) for a second sample counted from times t3 to t4 can be made consistent with the average rate Co determined for a first sample counted from times t1 to t2 by the relationship: N(e-»i-e-M») , , C2(f) " &-«,)(*-«.-«-»«) [21 in which N is the total number of counts taken and is the decay constant. RESULTS AND DISCUSSION The self-diffusion coefficients determined in this investigation are listed in Table 11. Values of the parameters used to calculate the coefficients are given in the table, as are values of the random counting error &apos; for the concentration ratio pz and the corresponding expected random variation AD in the diffusion coefficient. The quantity is calculable from: &apos;Cg — C2(t)} , „ ,2 .-„¦, M co-csl(ACs)J W in which AC is the error in the individual count rate. The mean values of the diffusion coefficients within each temperature group are also given in Table 11. Such temperature groupings of data are reasonable because of the small variations between the temperature~.~

Jan 1, 1970

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By C. S. Finney, John Mitchell

The growing popularity in the United States of the vertical-flue even was emphasized when in 1905 the United States Steel Corp. chose the Koppers oven as the type which best suited their requirements. Heinrich Koppers was born on November 23. 1872. at a small farm in Walbeck near Geldern on the lower Rhine. When young Koppers was eight years old, however the family moved away from the farm to the industrial city of Bochum in the Ruhr. Here Koppers attended public school and subsequently served an apprenticeship to a tinsmith before taking a job as a lathe operator with a local steel company. He had ambitions to be much more than a machinist, however, and used his week-ends and evenings to improve his theoretical background by taking courses at a vocational-training school in Bochum. After winning the highest honor the school could bestow (the silver Staats-medaille), Koppers went on to continue his education at the Rheinisch-Westfalische Hüttenschule in Duisberg. One of his teachers there, Fritz Wüst who later became a professor at the Technische Hochschule at Aachen, recognizing Koppers&apos; unusual abilities, predicted for him a great future. In 1894 Heinrich Koppers joined the firm of Dr. C. Otto and Co. in Dahlhausen, and in 1899 while superintendent of the Mathias Stinnes mine he built his first battery of ovens for Hugo Stinnes, the German industrialist. Two years later he started his own organization, and in 1902 he made Essen his headquarters. It was to Essen that a group of engineers from the United States Steel Corp. went in 1906 with an invitation to Koppers to design and supervise the construction of four batteries of ovens at the Joliet works of the Illinois Steel Co. Each battery was to consist of 70 ovens. Arriving in the United States in 1907, Koppers established a branch of his firm in Joliet, and construction began. The first battery was fired on July 27, 1908. Rugged and simple, these ovens incorporated basic design features which were to make the Koppers oven and its future modifications the choice of a very large segment of the by-product coking industry of America. The 280 ovens at Joliet were 35 ft long, 8 ¾ ft in height, and tapered from 21 to 17 in. The total daily capacity of the four batteries was 2240 tons of coke. The ovens were of the new cross-regenerative type; that is, instead of longitudinal regenerators serving an entire battery, as in the older Koppers ovens, cross regenerators for each separate oven were employed. Fuel gas was supplied from the side of the battery through ducts in the brickwork known as gun flues, which reached to the center of the battery under the vertical heating-flues. Removable, ceramic gas-nozzles fitted at the top of each gun flue helped to insure good control over the distribution of the fuel gas, and uniform heating conditions were also promoted by regulating the air supply to, and the suction in, each heating flue. A different refractory w& used for each battery. One was built of American silica brick, one of American quartzite, and two of imported German quartzite. The installation at Joliet proved to be very successful, and in 1911, 490 additional&apos; Koppers ovens were built for the Illinois Steel Co. at the great new steelworks at Gary, Ind. By 1912 the H. Koppers Co. had established its headquarters in Chicago and was rapidly extending its business to include construction for such iron and steel companies as the Woodward Iron Co. at Woodward, Ma. (80 ovens in 1912); the Tennessee Coal, Iron and Rail- road Co. at Fairfield, Ala. (280 ovens in 1912); the Inland Steel Co. at Indiana Harbor, Ind. (86 ovens during 1913 and 1914) ; and the Republic Iron and Steel Co. at Youngstown, Ohio (68 ovens in 1913). In 1914 a group of men in Pittsburgh bought a major shareholding in the H. Koppers Co., and moved the headquarters of the organization from Chicago to their own city. Under its new management the company was highly successful in obtaining a large share of the contracts for by-product installations built during World War I. In 1917 the remaining German interests in the company were

Jan 1, 1961

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

D. T. ROGERS*—The conclusions drawn in this paper have important practical significance to the steelmaker and the metallurgist if, in practice, it is demonstrated that metallic copper in the charge will pick up sulphur from the furnace atmosphere and thus increase the sulphur content of the bath. The problem of residual copper arising out of increasing copper in the scrap available to the industry is, in itself, a matter of concern to the steel maker. If, in addition to the often detrimental effects of high residual copper upon the physical properties of some important steel grades, there is to be a complication of the sulphur problem, then we have a set of conditions that bodes no good for the open hearth melter and the open hearth metallurgist. M. B. BEVER*— Investigations of gas-metal equilibria continue to be of interest, especially as new possibilities for improving experimental techniques emerge. Higher purity of reacting substances, better refractories, improved methods of temperature control and an increased awareness of the pitfalls of high-temperature equilibrium work are

Jan 1, 1950