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By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

By J. A. Putnam, A. D. K. Laird

In laboratory research on the behavior of oil, gas and water in porous materials, no direct method has been devised to measure saturation without disturbing the flow. Indirect methods involving various forms of radiation have been developed for measuring one or two components. The X-ray absorption method for two components has been described previously1-3. The possibility of three component measurement has also been mentioned1. Since two component measurement still requires considerable care to insure accuracy, the fact that three components can be measured satisfactorily is not generally appreciated. The fraction of the energy of an X-ray beam of one wavelength transmitted through a material is given by the transmission factor. in which 1 is the beam's path length through the fluid. p is the fluid density, and 1,. is its mass absorption coefficient. Eq. 1 implies that all parts of the beam pass through equal amounts of the fluid. Practical applications are, therefore, limited to systems in which the fluid is distributed so that I varies negligibly over the cross-section of the beam. Typical variations of the transmission factor with X-ray tube potential arc shown in Fig. 2 from which experimental points have been omitted for clarity. The X-ray absorption of low pressure gases in a core is practically zero so it cannot he distinguished from that a vacuum by instruments that will differentiate between liquids. The transmission factor of a gas in a core is. therefore, unity. Consequently, the saturation of only one gaseous component can be found. If two fluids completely fill a core, their two saturations add to unity and, therefore, only one value of the transmission factor, T, is needed to determine both of them. When two liquids do not completely fill the core, their saturations do not add to unity and transmission factors at two wavelengths must be measured. At one of these wavelengths, 7 for one liquid must be different from T or the other liquid. The change of T for one liquid us the wavelength is changed between the two values must be different from the corresponding change of T in the other liquid. The two values of fluid saturation will also give that of the gas because the three saturations must add to unity. In Fig. 2 it can be seen that there are many large differences of T between various oil solutions and water solutions at any one potential, and between potentials for any one solution. Consequently, conditions for optimum accuracy of measurement of the saturations of a gas and two liquids can be chosen. Once the operating potentials have been selected, however. it is more convenient to cross plot the data from Fig. 2 on transmission factor-solution concentration coordinates for the chosen potentials, as shown in Fig. 3. Fig. 3 was used to plan the experimental procedure for Core N-38-1. Since the voltage control at 45 kv was good, the slopes of the curves in Fig. 2 at this potential would cause little error. At low potentials, however, the voltage control was not good, so 33 kv was chosen because the small slopes of the curves made voltage control less critical. The lowest strength beam that could be measured reasonably at 33 kv corresponded to a minimum T factor of 0.385. Fig. 3 shows that both 4.80 weight per cent of cadmium chloride in water and 24.0 per cent of iodobenzene in crystal oil had this T value, and, consequently, were indistinguishable to the X-rays at 33 kv. Thus, at 33 kv, the liquid saturation was given by the same curve regardless of the relative amounts of oil and water solutions present. This simple calibration curve from which the gas and liquid saturation can be read, is shown in Fig. 4. Fig. 3 also shows that at 45 kv, T for the aqueous solution is 0.610. and that T for the oil solution is 0.220. These values were transferred to Fig. 4 to give the triangular calibration plot from which the brine and oil saturations can be found, after the gas saturation has been determined at 33 kv.

By V. J. Driscoll

A method is given for checking pore volume reserve estimates and transient water inflzix factors utilizing early well performance. Principal applications are based on the observation that there is a convenient transient time-range in terms of well spacing in which observed pressure drop will give a good indication of fluid-in-place. Primary quantity determined is a porosity-feet value applicable in the vicinity of an observation well. Checks on porosity or net pay thickness and permeability values also are obtained. These are particularly valuable in improving quality of interpretive factors entering into pore-volume reserve determinations for larger fields. In smaller fields, direct determination of total field reserves and approximate location of boundaries may be made in some cases. Well interference and production data plus a build-up curve on the observation well are needed. The build-up curve may be taken at any time. Field applications are given. The method can be applied with the completion of the second well on a new discovery or to older reservoirs by major changes in withdrawal rates from a local area. Appropriate test length permits results to be obtained with equal accuracy on widely spaced wells. Criteria for optimizing test conditions are given. Provision is made for various boundary and well effects including incomplete observation well build-up. INTRODUCTION Due to low quality data, initial pore volume reserve and water influx estimates may often vary by a factor of two or more from results obtained at a later date. Unfortunately, by conventional methods, more reliable answers from performance usually are not available until after most significant economic decisions have been made. Furthermore, in older reservoirs, uncertainties may still exist as to original oil-in-place, recovery factors and residual oil saturations due to incomplete or inaccurate performance data. This paper outlines situations and appropriate arrangements of basic transient theory whereby well interference data can be utilized to improve the quality of estimates under certain conditions. In addition to production data on offset producers, key information required is a measured pressure drop at an observation well, corrected for any incomplete build-up due to previous production, plus a formation capacity value derived from a conventional pressure build-up plot on the observation well. The method, as outlined, is strictly applicable only to a horizontal single-layered system of uniform rock characteristics containing a homogeneous fluid of low and constant compressibility. However, under the set of test conditions devised, requirements can usually be relaxed so that it should be applicable to most low permeability gas, water and undersaturated oil reservoirs. This is an area where more reliable information is certainly needed. BASIC CONSIDERATIONS A, B, C and F as subscripts or in the text refer to producing Well A, observation Well B, a more remote producing Well C and field boundary F. Combinations such as AB refer to distances and dimensionless times in terms of distances between these points, while single letters refer to distances and dimensionless times in terms of the well-bore or field radius. Equations covering definitions of quantities and complex situations are given in the Appendix. Key equations in practical units are given in Table 2. Transient Pressure Behavior Fig. 1 illustrates pressure drop at Point B with time due to initiation of a constant rate of withdrawal from Point A. This is shown as since a quantitative under-

By T. E. Scott, R. P. Zerwekh

The charactevistics of the deformatiotz of fcc thorium were examined between 78 and 473 K. Activation energy, actiuation volume, and the temperature dependence of the flow stress were determined and conlpared uith several theories for the rate-controlling mechnnistn of the tempemture-dependent component of the flou~ stress. It was established that the Cottrell-Stokes law does not hold, even approximately, for thorium. Through consideration of the above factors and other parameters, it was concluded that the vandom solute barrier theory proposed by Friedel demonstrates the best agreement with experimental observations of the deformation of thorium below ambient temperature. THORIUM, the first metal in the actinide series of rare-earth elements, is interesting and important from two points of view. In the more practical vein, it is a potential reactor fuel. As such, it is important to know its properties. Of specific interest here are the mechanical properties of thorium. Second, no detailed information concerning the deformation characteristics of the actinide elements has been gathered to date. In view of the interesting physical and chemical properties of these metals, their mechanical behavior might reveal characteristics which could improve our understanding of the mechanisms controlling deformation of the more common metals. For example, it has been shown1 that thorium exhibits a yield point which is greatly enhanced by interstitial solute elements such as carbon. This is not a normal occurrence in fcc metals. The goal of this investigation, therefore, was to characterize the deformation of polycrystalline thorium. MATERIAL AND PROCEDURES Thorium, made by the magnesium intermediate alloy process described by Peterson et al.,2 was rolled and swaged to 0.065-in.-diam wire. The metal analysis is given in Table I. After preparation, the oxygen and nitrogen contents had risen to 308 and 60 ppm, respectively. The 0.065-in.-diam wires were cut into 2-in. lengths and annealed in a vacuum of lo-' Torr at 750°C for 1 hr, producing a grain size of 2735 grains per sq mm. The ends of the 2-in. sections were masked off so that a 1-in. gage length could be electropolished. Specimens were polished at 35 v in a solution of 6 pct perchloric acid in methanol which was maintained at 0°C . The gage diameters after polishing were about 0.0625 in. The tests were run on a screw-driven tensile machine at a constant crosshead speed corresponding to a strain rate of 0.005 min-'. The strain rate was changed rapidly after each 0.01-in. extension between 0.005 min-' and one of three higher strain rates which were selected in order to achieve strain-rate ratios of 5, 10, and 20. Tests were run at several temperatures from 78" to 473°K; most were tested at 423", 300°, 215", and 78°K. EXPERIMENTAL RESULTS Flow Stress vs Strain and Temperature. Typical true stress-true strain curves for thorium are shown in Fig. 1 for several temperatures over the range 473" to 78°K. The curves for 78", 215", 300") and 423°K were obtained from strain-rate change tests using the lower (0.005 min-') or base strain-rate values of stress. Additional tests, using the same base strain rate at different strain-rate ratios, gave curves which virtually superposed on those shown, indicating that strain-rate changes did not materially influence the work-hardening characteristics at the base strain rate. The curves for 273") 373") and 473°K were standard tensile tests at 0.005 min-'. The behavior of the flow stress with temperature is

Jan 1, 1968

J. B. Cohen (AVCO Mfg. Co.)-The model presented by the authors is only one of several possible mechanisms for low-temperature aging. It is true that the motion of dislocations to the copper atoms, followed by diffusion along the dislocation lines, is one such mechanism. However, the details of such a process which would :result in copper-rich platelets on (100) planes in the f.c.c. matrix are not clear. Furthermore, there is at least one other mechanism that may be used to e.xplain the authors' results, so that the data do not clearly favor the Turnbull model. The zones may form by "normal" diffusion. The diffusion constants would be higher at room temperature than extrapolated data would suggest due to vacancies trapped in the specimens in the quench. The diffusivity would then be multiplied by the ratio of the number of vacancies present at the solution temperature to that present at room temperature. These vacancies could remain in the alloy specimen for long times at room temerature, due to interaction with the copper atoms. ' The activation energy for diffusion is smaller than that for bulk diffusion at elevated temperatures for it is only that for the motion of vacancies existing after the quench; after these are used up, the aging process effectively ceases. It is somewhat questionable if the laws governing transformation kinetics can be directly applied to changes in elastic moduli, especially in the case of aging where the structure and the composition of the zones may be changing during aging, If such laws are assumed, it is possible to explain the exponential factor of % with this vacancy model. It is probable that the structure of the zones and the matrix match only on (100) planes. Certainly the precipitates that form in this system after various aging treatments show orientation relationships similar to those of the zones. Strains on the edges of the zone may set up fields which do not allow the zone to grow in an edgewise manner. The exponent in the growth of a thin plate in a direction perpendicular to its face would be %. It may also be that copper atoms are attracted to dislocations. If this is the rate-controllin factor in the growth process Ifthisthen an exponent of % or % may arise. The writer would like to know if the authors have tried plotting l/a; proportional to as might be expected for "dislocation drainage." R. H. Doremus (General Electric Research Laboratory)—An important new method for following the growth of Guinier-Preston zones is presented in this paper, and I wish to congratulate the authors on their experiments. Their interpretation of the results, however, is doubtful in certain respects. To determine the exponent m in Eq. [4] the authors plotted -log at against t to various powers (their Fig. 6). The initial value of frequency used for these plots was found by extrapolating the data to zero time. In Fig. A the data from their Fig. 2 are plotted against a linear, rather than logarithmic, time scale. To obtain graphs similar to their Fig. 6 for these data one must use an initial frequency of about 52720; such a plot for m = % is shown in Fig. B. The straight line in Fig. B fits the data in an intermediate range only. The curve drawn in Fig. A was mapped from this line; comparison of

Jan 1, 1960

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

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

Jan 1, 1955

By A. R. Gregory, M. R. J. Wyllie

The literature reveals that scant attention has been paid to the systematic experimental determination of the formation factors of unconsolidated porous media. No experiments appear to have been made on the effect of increasing cementation on the formation factor of an initially unconsolidated porous medium. Measurements have accordingly been made of formation factors as a function of porosity for aggregates of spheres in the porobity range 12-56 per cent and of cubes, cylinders, discs and triangular prisms in the porosity range 30-45 per cent. The results are examined in the light of the theoretical equations of Clerk Maxwell. Fricke and Slawinski. Aggregates of unconsolidated spheres and beach sands have been artificially cemented with silica and the formation factor-porosity relationships determined. A theory is outlined which seeks to explain the results obtained and which postulates that formation factor and porosity data for consolidated sandatones may be used to determine the original porosity of the unconsolidated sands from which the consolidated sandstones were derived. It follows also that for consolidated sandstones F' = C where F is formation factor, fractional porosity and C and k are constants. INTRODUCTION All schemes of electric log interpretation implicitly or explicitly require the use of formation resistivity factors or? as they are now generally called. formation factors. 'The originator both of the concept of formation factor and of the use of formation factor data in electric log interpretation was Archie.' More recently it has been suggested that formation factors are of value in describing fluid flow in porous media. A full discussion of this problem together with adequate reference.: has been given by Wyllie and Spangler.' In spite of the theoretical and practical importance of the subject, there appear to be remarkably few basic formation factor data in the petroleum literature. A wider search reveals that this situation is nut confined to the literature of the to industry. at various times over the last century, attempts have been made to compute the theoretical relationship between the formation factor and porosity of simple systems of unconsolidated particle.. However. the formulae derived are not all identical and the experimental evidence adduced in support of each i; not wholly convincitng. Most of the experimental work has been carried out on system. of unconsolidated spheres, although some attention has been given to systems of spheroids and cylinder. Other simple shapes have received neither theoretical nor experimental investigation. The writers feel that a better understanding of the formation factors of complex systems of practical importance requires a firm foundation of reliable experimental data applicable to simple systems. Accordingly, they have reviewed the relevant literature and have determined experimentally the relationship between the formation factor and porosity of unconsolidated aggregates of particles of regular geometrical shapes. Some experiments have also been carried out to investigate the effect of cementation on the formation factor-porosity relationship. PREVIOUS WORK Although the term formation factor was not used. the relationship between the resistivity of a solution containing dielectric solids and the resistivity of a similar solution not containing solids is an old and important problem. The formation factor of a system of dispersed spheres as a function of porosity was considered by Clerk Maxwell. Maxwell arrived theoretically at the following expression: where F is formation factor and fractional porosity. Lord Rayleigh' also examined the problem of the formation factor of systems of spheres and cylinders and concluded that for spheres Clerk Maxwell'.; expression gave a value of F whirl]. at low porosities particularly, was too small. However,

Jan 1, 1953

By F. Forscher

Pronounced porosity, decreasing with distance from the fracture surface, is found in the necked region of tensile specimens tested at room temperature or liquid nitrogen temperature. A hydrogen solution treatment followed by a quench prevents pore formation in tests at —196°C, but has little effect on tests made at room temperature. Reduction of area values at —196°C are strikingly improved by the same treatment, but show no improvement in room temperature tests. The experimental results support the hypothesis that strain-induced porosity results with hydride initially present or, in material containing less than 50 ppm H, with hydride precipitated by strain aging. ZIRCONIUM'S advent as an engineering material in nuclear reactor construction has brought forth many investigations concerned with the properties of this metal and its alloys. Some attention has been given to the ductility of the metal.1, 2 Particularly, the effect of hydrogen on the impact strength was noted," indicating a pronounced dependence of ductility on the hydrogen content and its distribution in the metal. Micro graphic:' and X-ray diffraction studies' have shown that a precipitated hydride phase causes embrittlement in zirconium,' which implies a distinctly different mechanism from that causing hydrogen embrittlement in steels."-' In the latter case, it is assumed that atomic hydrogen diffuses to rifts, where it forms molecular hydrogen under such internal pressures that it causes the rifts to enlarge, leading to fracture. Thermo-dynamic studies of the Zr-H system8, 9 also indicate that the internal pressure of molecular hydrogen would be too low to cause any damage to the zirconium at room temperature, and the formation of a zirconium hydride (d phase) is favored." It is noteworthy that this phase has a face-centered-cubic structure and nearly 18 pet larger molar volume than close-packed-hexagonal a-zlrconlum' Other features of the ductility of zirconium are the absence of a typical cup-cone failure upon tensile testing, a pronounced strain-induced porosity in the necked region of a tensile bar, Fig 1, and the associated spongy appearance of the fracture surface A tremendous improvement in ductility at liquid nitrogen temperature can be observed following a heat treatment that retains the commonly present quan- tities (10 to 50 ppm) of hydrogen in solution. Such tests show a typical cup-cone failure and the absence of strain-induced porosity, Fig. 2. The present paper reports results of an investigation into the causes of strain-induced porosity in zirconium. Room temperature tensile fractures of mild steel, aluminum, and titanium have also been examined for strain-induced porosity. In each case porosity could be detected, but the amount was orders of magnitude less than was found in zirconium. Of the three metals, titanium showed the strongest effect. Material, Specimens, and Preparation The greater part of this investigation was done on Westinghouse crystal bar zirconium, are-melted, forged, and hot-rolled. Chemical analyses of the hot-rolled plates are given in Table I, along with those of the Foote crystal bar zirconium used in this work. The specimens were machined from the hot-rolled plate (1550°F) of 1/2 in. thickness and subsequently heat-treated according to one of the treatments shown in Table IS. All specimens were machined round, the longitudinal axis in the rolling direction, with a gage

Jan 1, 1957

By M. G. Benz, J. F. Elliott

A. J. Goldak and J. Gordon Parr (U)iuersity of Alberta) —Margolin and Ence's paper reached us only a few days after we had submitted a paper on the structure of Ti2Cu to the AIME. Here, however, we only wish to point out an error in the paper (page 321): "Karlsson has reported the crystal structure of the first intermediate phase occurring in the Ti-rich portion of the Ti-Cu system to be face-centered tetragonal." Karlsson actually reported the structure of Ti3Cu (i.e., "the first intermediate phase") to be primitive tetragonal with four atoms per lattice point: Cu at 0, 0, 0; and Ti at 1/2, 1/2, 0; 0, 1/2, 1/2; and 1/2, 0, 1/2. Thus, Karlsson suggests a primitive lattice with an ordered arrangement of atoms located at corners and face-centers: Ence and Margolin suggest a random body-centered tetragonal structure—-with which our results agree. E. Ence and H. Margolin (authors' reply)— We do not agree that Karlsson has not reported the structure of Ti3Cu as face-centered tetragonal. The fact that Cu atoms are located at the corners and titanium at the face-centers does not indicate that the lattice is not face-centered. We are pleased that the discussers' results agree with our own.

Jan 1, 1962

By H. Margolin, E. Ence

A. J. Goldak and J. Gordon Parr University of Alberta) —Margolin and Ence's paper reached us only a few days after we had submitted a paper on the structure of Ti2Cu to the AIME. Here, however, we only wish to point out an error in the paper (page 321): "Karlsson has reported the crystal structure of the first intermediate phase occurring in the Ti-rich portion of the Ti-Cu system to be face-centered tetragonal." Karlsson actually reported the structure of Ti3Cu (i.e., "the first intermediate phase") to be primitive tetragonal with four atoms per lattice point: Cu at 0, 0, 0; and Ti at 1/2, 1/2, 0; 0, 1/2, 1/2; and 1/2, 0, 1/2. Thus, Karlsson suggests a primitive lattice with an ordered arrangement of atoms located at corners and face-centers: Ence and Margolin suggest a random body-centered tetragonal structure—-with which our results agree. E. Ence and H. Margolin (azlt1zo.l-s' reply)— We do not agree that Karlsson has not reported the structure of Ti3Cu as face-centered tetragonal. The fact that Cu atoms are located at the corners and titanium at the face-centers does not indicate that the lattice is not face-centered. We are pleased that the discussers' results agree with our own.

Jan 1, 1962

By W. R. Purcell, C. S. Brooks

The internal surfaces of rocks which are in contact with interstitial fluids are known to influence in some degree the recovery of hydrocarbons from pay zones. Despite the admitted importance of the influence of solid surfaces on hydrocarbon recovery, little information is available concerning the extent of surface of reservoir rocks. In this paper a description is given of the apparatus and procedure employed in the determination of the surface areas of sedimentary rocks, and values are reported for a variety of sandstone and limestone cores. In addition, consideration is given to the Kozeny equation, which relates surface area to porosity and permeability. A colliparison is made between the surface areas as calculated from this equation and the geometrical areas of a series of packs of spherical glass beads. Also, for a group of sandstone cores. Kozeny areas are compared with surface areas as determined by the gas adsorption method employed in this investigation. INTRODUCTION It has long been recognized that many processes which are of importance to hydrocarbon production are controlled in some degree by the extent of the surface of the reservoir rock through which the hydrocarbons move. For example, the recovery efficiency that is obtained in a given reservoir is certainly determined in part by the action of interfacial forces between the reservoir fluids and rock, and this action is influenced in turn by the extent of solid surface. Despite the admitted importance of surface effects to problems of petroleum recovery, little information is available concerning the extent of surface of reservoir rocks." It is the purpose of this paper to describe an apparatus which has been employed for the measurement of the surface areas of rock samples and to present the values which have been obtained for a variety of sandstone and limestone cores. In addition, the relationship of surface area to permeability and porosity, as given by the Kozeny equation, will be discussed. METHOD OF MEASURING SURFACE AREA The method of determining surface areas as employed in this work has previously found wide use in studies of porous solids such as catalysts. The method involves the measurement of the amount of physical adsorption of an inert gas, such as nitrogen or argon, on the bare surface of the solid at reduced pressure and constant temperature near the normal liquefaction temperature of the gas. With the aid of the theory of isothermal adsorption as developed by Brunauer, Emmett, and Teller,' it is possible to ascertain the amount of gas (and hence the number of molecules) which is required to cover the solid surface with a single layer of molecules. From a knowledge of the covering area per molecule the total surface ares of the solid can be computed. Since the Brunauer. Emmett, Teller (BET) theory has been adequately discussed elsewhere: it will suffice here merely to present their final equation as ordinarily employed for surface-area calculations. This equation relates the volume of gas, V, which is adsorbed at pressure, P, to the liquefaction pressure, Po, of the gas, and to the volume of gas, V.,, that is required to form a monomolecular layer: In this equation C is a quantity which is related to the heats of adsorption and liquefaction of the gas; for a particular solid-gas system at Constant temperature, C is considered to have a constant value. The basic adsorption data can be presented in the form of Equation (1) by plotting the quantity P/V(Po- P) as a func-

Jan 1, 1952

By Charles Jones

Discussion of the paper of CHARLES COLCOCK JONES, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 105, September, 1915, pp. 1887 to 1898. D. A. LYON, Salt Lake City, Utah.-For some years I have been interested in the iron-ore deposits of the Pacific Coast, and I feel very much indebted to Mr. Jones for the information he has given us on this subject. I think that we are also very much indebted to him for having presented this paper, as he has given us reliable data in shape of facts and figures, which is just what we need in considering whether or not it would be commercially feasible to attempt to establish an iron and steel industry on the Pacific Coast. Personally, due to lack of market, I do not think it is a commercially feasible proposition at the present time. Mr. Jones states that pig iron can be produced on this coast as cheaply as it can be produced in Pittsburgh. Even. so, what can be done, with it after it is produced? To begin with, iron produced on the. Pacific Coast has to compete with iron produced in China. Last year I had occasion to investigate the subject of the market for iron and, steel on the Pacific slope, and found that it was possible for the producers of Chinese iron to sell it for much less than the price for which iron can be produced in the West, and also for less than eastern pig iron is now sold for, even when shipped through the Panama Canal. I was informed that the agents for Chinese iron had instructions to sell it for $1 or $2 less per ton than that asked for other irons on the market. Of course, I realize that the competition of Chinese iron may not be important, but even if it is not, and even though pig iron ,can be produced at the cost given by Mr. Jones in his paper, I do not see any immediate chance of its being so produced, due to lack of market. C. C. JONES, Los Angeles, Cal.-Mr. Lyon is right. It is a fact that Chinese pig is being sold in San Francisco on some large contracts at $18.50 a ton, while $19 is the usual price. We ought to produce iron. on this coast at $14. Personally I do not think Chinese iron is ever going to be an important factor. It is a bugbear out here now. You are not going to have much Chinese pig iron in .this country. Our little friend Japan is going to absorb everything it can. The price of Chinese pig iron at $18 is about as low as it will ever get. If we can show you that we can produce this iron here at the same price as at Pittsburgh, I. think you will have a good opportunity to compete with anything China or India can ever do. Costs there are very low now. They are going to come up by leaps and bounds in the next few years. The labor cost over there may be very low now, but I. have seen some men from there quite recently

Jan 12, 1915

By J. Intrater, E. S. Machlin

In a study of grain boundary sliding in superpure Copper (99.999 pct),&apos; bicrystals of a specific shape were used, Fig. 1. That shape was adopted in order to minimize the deformation of grains on both sides of the boundary due to clamping. Another requirement was to obtain bicrystals with a rnicroscopically straight boundary, Fig. 2. Single crystals of predetermined orientation (growth axis parallel to <310>) were grown in a graphite mold from seed crystals. The apparatus for growing single crystals consisted of a vacuum system, argon purification train, vycor tube (in which a graphite mold was placed), a carriage for the induction coi1,and a Lepel (7-1/2 KW) high-frequency converter. The graphite mold was heated by induction and the charge in turn was heated by conduction. The induction coil was moved by means of a motor at a speed of 1 1/2 in. per hr. Single crystals of two different orientations were grown from the melt in one-half of a split graphite mold, Fig. 3(a). Two such crystals were then placed in contact with each other in another split mold, Fig. 3(b) using tapered inserts. The pair of crystals was then remelted starting 2 in. from the top to insure that the whole top portion of the crystals was maintained molten. By moving the induction coil

Jan 1, 1960

By W. Spencer Hutchinson

THE relative importance of mineral production in British South Africa is about as follows: Gold, $200,000,000; diamonds, $40,000,000; coal, $18,-000,000; asbestos; $3,000,000; chrome ore, $2,000,000. In 1926 the gold mines paid $42,000,000 in dividends, the diamond mines $13,000,000, coal nearly $3,000,000, others less than $500,000. The recorded history of South Africa starts with the visits of the Dutch and the English in the sixteenth century, followed by the settlement of Cape Colony by the Dutch East India Company in 1651: The English acquired Capetown in 1806 and conflicts between English and Boers were a part of the history, from that, time on. Transvaal was settled in 1835, following the Great Boer Trek. The mining of diamonds became im-portant in 1870; the production of gold from the Rand in 1890;&apos; the export of chrome ore in 1910; and the dis-covery of platinum in 1925. South Africa has a race problem, resulting not alone from the disparity of numbers between whites and natives, more than seven blacks to each white, twenty to one in Southern Rhodesia, and three. hundred to one in Northern Rhodesia; but because of the division of the white race between English and Cape Dutch or Afrikaans. The natives are also of many tribes.

Jan 6, 1927

By L. H. Wolfe, J. O. Thieme

The tensile and shear strengths of frozen soil and the compressive strengths of ice and frozen soil were measured These tests showed that the strength of ice and of frozen soil increased as the temperature was decreased. A method is presented for the measurement of thermal conductivity and specific heat of earth and ice. Using the parameters thermal conductivity, specific heat and density, the thermal diffusivity was calculated. Results of thermal property tests establish water as the major variable contributing to thermal property values. INTRODUCTION During the last few years, a considerable interest has developed in underground storage of cryogenic liquids such as liquid natural gas. Because of its economy and safety, underground storage is being used. Before underground caverns could be seriously considered, however, the strength and thermal characteristics of the soil had to be obtained. Methods are presented herein for measuring tensile, compressive and shear strengths, specific heats and thermal conductivities. The tests were performed on two soils at temperatures from ambient to -195C. Because it is difficult to find data in the literature that pertain to a particular soil, ice was used to evaluate some of the experimental procedures. Some of our ice data are compared to the published values. PHYSICAI, PROPERTIES SOIL SELECTION AND SAMPLE PREPARATIONS The physical and thermal tests were performed on recompacted samples of two typical soils that might be encountered in underground caverns: a gray, fire clay that had been pulverized and mixed with water into a pliable mud; and a brown, sandy silt that was dug from a dry river bank and subsequent1y mixed with tap water. The moisture content of the test specimens was 17 to 22 per cent (based on the wet weight of the soil). This amount of water nearly saturated the silt, but the clay was well below the saturation point. The soils are partially described by the sieve analyses (Fig. 1) which show the particle size distribution of the coarser than 44 micron portion of the soils. The curves also show that approximately 75 per cent of the clay and 20 per cent of the silt are finer than 44 microns. The particle size seems to affect some of the physical properties, and the finer than 44 micron portion is important in the thermal conductivity test. Physical specimens were cut with a bandsaw from frozen blocks of the soil. The specimens were then sanded and kept frozen until after they were tested. They were stored at the approximate test temperature for several hours. Then, to equilibrate the samples to the test temperature, they were stored at the temperature at least an hour before they were tested. TEST EQUIPMENT An Instron, which is a constant speed gear-driven instrument, applied force to the samples and drew stress-strain plots of the test. All of the samples were strained at 0.02 in./min. All of the physical tests were conducted in a temperature cabinet that controlled the temperature to 1C. TENSILE STRENGTH Briquette or "dog-bone" shaped tensile specimens were pulled with suitably shaped jaws. This shape of specimen, which is usually used for tensile tests of concrete, is satisfactory for testing frozen soils except that the samples tend to

Jan 1, 1965

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

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

Jan 1, 1955

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,&apos;who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

[ ] [LOCAL SECTION CODE (Numbers indicate Sections) No. Section LI Alaska L50 Adirondack L2 Arizona L58 Arkansas L84 Balcones L66 Billings Petr. L3 Black Hills L4 Boston L76 Caracas L5 Carlsbad Potash L6 Central Appal. L60 Central N. Mex. L7 Chicago L79 CIM-AIME Calgary L82 CIM-AIME Edmonton L8 Cleveland L9 Colorado]

Jan 1, 1961

By W. R. Phibbs

The blast furnace of the Columbia Steel Corpn., at Ironton, Utah, was put in blast April 30, 1024, and its operation has presented some interesting problems. The coke for the furnace is furnished by 33 Koppers Becker type ovens of 15 tons capacity each. The coal is shipped from the company&apos;s mine at Columbia, Utah, which is approximately 123 miles from Ironton, and is probably the highest volatile coal that is being coked for blast furnace use in this country. The analysis of the coal is: PeR Cent. Moisture................................................. 3.90 Volatile.................................................. 39.00 Fixed carbon............................................ 51.10 Ash............................................... 6.00 Sulfur................................................. 1.07 The analysis of the coke is: PeR Cent. Volatile.................................................. 0.55 Fixed carbon............................................. 89.70 Ash...................................................... 9.75 Sulfur................................................... 1.05 The coke is light and of a fingery construction, but is very fast burning. A screen test of the coke as loaded into the skip tubs at the furnace shows the following: Per Cent. On 2 in.................................................. 17.90 On 11/2 in................................................ 41.78 On 1 in.................................................. 27.80 Through 1 in............................................. 12.52 The by-product yields are as follows: Gas................................. 11,000 cu. ft. per ton of coal Sulfate............................... 30 Ib. per ton of coal Tar.................................. 12.65 gal. per ton of coal Motor fuel........................... 3.00 gal. per ton of coal Average B. t. u. in gas................. 567

By R. E. Cole, A. M. Gaudin

OLEIC acid, a standard flotation reagent, has generally been preferred to other fatty acids. Because oleic acid differs from saturated fatty acids by the presence of one carbon-to-carbon double bond and because the flotation operation is one in which extremely intimate exposure of the reagent to oxygen is obtained, it appeared possible that the value of oleic acid as a flotation collector was related to the oxidizability of its double bond. To test this hypothesis, the floated mineral, fluor-ite, was leached with a solvent capable of extracting the adsorbed reagent and the extract was analyzed.&apos; Results show that oleic acid is not oxidized during flotation, although some oxidation can be obtained if the flotation operation is repeated many times and if oxygen in place of air is employed as the gas during flotation. Incidentally, it was found that lino-leic acid which has two nonconjugated double bonds is not affected appreciably more than oleic acid. Linolenic acid which has three nonconjugated double bonds is measurably altered even during one flotation step, using air. The fatty acids used, from the Hormel Foundation, were of the highest purity. The quantity of fatty acids employed in each test was sufficient to float the mineral, but less than the theoretical amount required to form a monolayer at the mineral surface. The purpose of this limitation was to eliminate droplets of oil smeared on the adsorbate-covered mineral surface. The mineral was dried in vacuum at about 60 °C. Effective leaching was obtained by use of a solution of 1 pct hydrochloric acid in absolute alcohol. The extract was separated from the solvent by distillation, with final recovery of the extract in carbon tetrachloride. The identity of the extract was tested by a combination of analytical procedures including infrared spectroscopy, saponification number, iodine number, and index of refraction. At the outset, great hopes for accurate quantification of oleic acid oxidation had been entertained in regard to the method of infra-red spectroscopy. Unfortunately, because the double bond in the oleic acid is so sym- metrically located at the center of the molecule that it provides very weak absorption bands, accurate quantitative analyses were not obtained. Nevertheless, infra-red spectrograms suggested the absence of double-bond oxidation during flotation. Iodine number, semi-micro method, provided a critical test of the extent to which fatty acids oxidized during flotation, see Table I. The index of refraction was used in a qualitative rather than quantitative fashion, and its findings corroborated those obtained by the iodine-number method. It is concluded, in the case of fluorite and C-18 fatty acids having one or two nonconjugated double bonds, that there is practically no change of the fatty acid molecule or ion during the flotation operation. It would appear, therefore, that the extraordinary utility of these reagents is related to some property of the compounds other than the oxidizability of their double bonds. Acknowledgment The research reported herewith was sponsored by the Research Division, U. S. Atomic Energy Commission, and for this help the authors express their appreciation. Reference &apos;R. E. Cole: "Double-Bond Reactivity of Oleic Acid During Flotation." Thesis submitted in partial fulfillment of the requirements for the degree of M.S. at the Massachusetts Institute of Technology.

Jan 1, 1954