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By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By E. J. Pasierb, H. W. Paxton

Mavkers ill a diffusion couple in the iron-chromium system move towards the high chromium side indicating Dcr > DFe at the marker composition. By a combituztion of measurements of D& and D a: a function of composition, this is also shown independently. DFe is calculated as a function of composition. and shown to be in reasonable agreement with measured values by other workers. MEASUREMENTS of marker movements in diffusion couples have been used from time to time to demonstrate that a vacancy or interstitial mechanism may be operative. Since there is a possibility that ring diffusion1 may be operative in chromium, the present experiments are of interest in showing some non-ring mechanism in iron-chromium alloys around the equiatomic composition. EXPERIMENTAL PROCEDURE The movement of markers originally at the interface between 1-in. sq sections of pure Cr (6 mm thick) and outer slabs of 30 Cr-70 Fe alloy was followed as a function of time at temperatures from 1150" to 1425"C, in a Kanthal-wound furnace. Temperature control was +5°C over extended periods. The analyses of these alloys are given in Table I. Selection of suitable markers presented a considerable experimental problem; the eventual solution was to draw quartz rod down to 0.01 cm and seat this in V-grooves 0.01 cm deep on each side of the chromium prior to welding. A preliminary experiment in which the groove was machined in the alloy gave identical results. Welding was accomplished by passing a heavy current through specimens under moderate pressure in a helium atmosphere. This method produced good welds with a planar interface as shown by subsequent metallo-graphic investigation. Any markers which did not adequately fill their groove and showed subsequent contamination from the atmosphere during heat treatment were not considered reliable. The composite sample was ground and metal-lographically polished on the four sides perpendicular to the interface. Fiducial marks (deep milled slots) were made outside the diffusion zone to check on total volume change. All necessary measurements were made on a metallograph reading to +0.0005 cm. The samples were wrapped in tantalum foil and given diffusion anneals for times to 200 hr in carefully purified dry hydrogen in a sealed McDanel porcelain tube. Chromium-zirconium chips were introduced near the specimen as an additional getter. The specimens were cooled relatively slowly after the diffusion anneal to preserve the McDanel tube but no significant error in effective time at temperature was thereby introduced. At least 1 mm was ground off the surface before measurements were taken. It was observed that the grain size following short diffusion anneals was several mm and was appreciably larger in the 30 Cr alloy than in the pure Cr. No significant grain boundary penetration was present as indicated by the etch limit. The results are presented in the next section. Measurements of D were made by standard sectioning techniques with chemical analysis. Machining difficulties limited the

Jan 1, 1961

By E. H. Snow, B. E. Deal

Instability effects in semicanductor devices have long been attributed to the motion of charges on or within oxide layers on the surface. These effects are of critical importance in metal-insulator-semiconductor MIS) field-effect devices. For this reason, the capacitance-voltage or the conductance-voltage characteristic of these devices can be used as a sensitive detector to study charge transport and polarization effects in the oxide or insulator. A review is given of the results of such studies of thermally grown SiO2 as well as of other insulating films of importance in silicon technology. Three types of effects are distinguished. The first of these is the drift of mobile cations within the dielectric, examples being thermally grown SiO, which is often contaminated with sodium ions, and a variety of other glasses in which the mobile ions are a part of the glass composition. The second effect is a dipole-type polarization which occurs in phosphosilicate glass films obtained by reacting P2O5 with thermally grown SiO2. The third effect involves the transfer of charges between the dielectric and the silicon electrode. This occurs in silicon nitride and other deposited dielectrics. It is concluded that MIS studies have provided a powerful technique joy the study of charge transport and polarization effects in insulating films. The knowledge gained from these studies has led to an understanding of surface effects on conventional transistors and diodes as well as making possible stable MIS transistors. THE metal-insulator-semiconductor field-effect transistor is conceptually the oldest type of active semiconductor device.' The earliest attempts at making this device were frustrated because of high surface state densities at the interface between the semiconductor and the gate insulation.' However, by using a silicon substrate with thermally produced silicon dioxide as the gate insulation, this problem was solved and metal-silicon dioxide-silicon devices with good characteristics were made as early as 1960. 3 Yet it was still over 5 years before these devices became a commercial reality. This delay was largly due, not to surface states, but to stability problems associated with polarization effects within the insulating layer which caused the threshold voltage of the device to drift under temperature and bias treatments. The solution to these problems has not only made possible stable MIS devices, but it has added immensely to our understanding of failure mechanisms in conventional bipolar transistors and has added to the reliability of ali types of planar devices. In this review, we shall first describe the effects of various types of polarization phenomena on MIS device characteristics. Then, since thermally grown SiO, is by far the most important insulator used in these devices, we shall review historically the type of instabilities which have been observed in thermal oxides, the attempts at understanding and eliminating them, and the present status of the problem. We shall then turn our attention to the various deposited insulators which have been used, including lead glasses, phosphosilicate glass, vapor-deposited silicon oxide, and silicon nitride. Interestingly enough, many of these materials show polarization effects which are quite different from those generally observed in thermally grown SiO2. THE EFFECTS OF POLARIZATION PHENOMENA ON MIS CHARACTERISTICS The simplest MIS device and the one which has been most frequently used in the study of polarization effects is the MIS capacitor. Two modifications of this structure with single- and double-layer dielectrics are illustrated in Figs. l(a) and (b), respectively. The capacitance of this structure as a function of voltage applied to the metal gate electrode is plotted in Fig. 2 for the case of an n-type silicon substrate. When the silicon surface is accumulated (positive bias) the measured capacitance is just that of the insulating layer C. When the surface is inverted (negative bias), the capacitance is that of the insulator and a silicon depletion layer in series CoCs/(Co + Cs). Indicated on the horizontal axis of Fig. 2 is the voltage VT at which the silicon surface becomes strongly inverted. This voltage corresponds to the threshold or turn-on

Jan 1, 1969

By Jack C. Haptonstall

This paper describes the analytical characteristics of Western subbituminous coal and the manner in which these characteristics apply to their use in a utility-sized steam generator. It compares these characteristics with those of typical Midwestern coal and Eastern bituminous coal. The paper also reviews in detail the design considerations that must receive attention when various blends of these three coals, or any combinations thereof, are planned to be used. This research paper describes variations in analytical and utilization characteristics when coals from different origins are blended in order to achieve a predetermined sulfur content for the purpose of predicting sulfur oxides emissions as they affect environmental regulations and the resulting alterations in utilization characteristics such blending would cause, and how such blends of coal would affect a utility-sized steam generator.

Jan 1, 1979

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan's theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By K. D. Jacob, W. L. Hill

Fluorine recovery in the United States has been restricted chiefly to manufacture of ordinary superphosphate and wet-process phosphoric acid. However, there is an expanding use of fluorine by industry in the form of hydrofluoric acid. Improved methods for recovering fluorine from phosphate rock would yield an adequate supply of fluosilicates and a substantial contribution to the hydrofluoric acid requirement. THE bulk of natural phosphates is comprised of calcium phosphates, which are usually apatites;' calcium aluminum phosphates such as pseudowavel-1ite; and aluminum phosphates, which occur in extensive deposits, notably on Grand Connetable Island." Nearly all deposits of current commercial value are apatite, often with admixed material of other classes. In the trade coarsely crystalline material, mainly fluorapatite of igneous origin, moves as apatite, whereas the fine-grained material of sedimentary origin is marketed as phosphate rock. The latter classification includes the phosphate shales in western North America. Although several genetic varieties of phosphate rock are recognized, most known reserves are of marine origin. Calcium phosphate is concentrated from Florida land pebble and Florida hard rock deposits and from Tennessee brown rock deposits. Phosphate Rock as a Fluorine Carrier: More than two decades ago Reynolds and Jacob surveyed the fluorine content of commercial phosphate rock from various parts of the world. Later these samples were re-analyzed by a new and more reliable method of determining flourine. The revised results with interim additions of new samples, published a few years ago in a brief summary," are shown in Figs. 1-3. Through the points representing the respective varieties of rock medial straight lines are drawn. In some instances the lines are well defined by the points; in others, where scattering renders the position of the best line uncertain, the greater weight is given points near the end of the covered range. Wherever distinct varieties are not recognized among regional deposits the custom is to identify the sample with the geographical location of the deposit. Although all rock varieties cannot be classified with certainty, the plotted results exhibit three distinct types of rock in which the F to P2O5 ratio diminishes, remains sensibly constant, and increases, respectively, as the grade of rock increases. Existence of two types of Florida land pebble, Fig. 1, is supported by additional results recently supplied by a producer." Generally speaking, phosphate rock from continental deposits carries considerably more fluorine, and apatite and insular phosphates less, in proportion to the phosphorus content than is required by the formula for fluorapatite. Exceptions to this are apatite from Canada and certain samples of Florida waste-pond phosphate. The manner in which excess fluorine is held and the nature of the carbonate in carbonate apatite are discussed in recent articles. High-grade calcium phosphates with F to P2O5 ratios less than 0.05 have been found in Curacao, Christmas Island," Mexic,13 and elsewhere. The calcium aluminum phosphates and aluminum phosphates aften carry notable amounts of fluorine. The F to P2O, ratio for one sample of pseudowavel-lite concentrate was 0.05." Aluminum phosphate from Grand Connetable Island is very low in fluorine, whereas some aluminum phosphate minerals" carry as much fluorine as highly fluorinated phosphate rock. Fluorine in Domestic Phosphate: The curves shown in the figures permit interpolation of the F to P2O5 ratio corresponding to the midpoint of selected ranges in grade of any one of the several varieties of phosphate. Multiplication of the interpolated ratio by the mid-range grade (P2O5) yields a figure for the percentage of fluorine in this grade. Then, with the use of the mid-range grade, the amount of fluorine held in phosphate reserves can be estimated, see Table I. Accordingly, on Jan. 1, 1950, the fluorine complement of known domestic reserves exceeded 420,000,000 long tons of the element. A previous figure," deduced in 1940 by a simpler procedure

Jan 1, 1955

By James K. Stanley

PREFERRED orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.1 In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurgical literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanical properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important in- formation, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational under- standing of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing 'stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required-it is only necessary punch or machine a disk of the sheet material and insert it into the testing device.

Jan 1, 1943

By L. R. Raymond, J. L. Hudson

This paper proposes a comparatively short-term (8 to 10 hours) well test for detecting and characterizing well-bore damage and for measuring mean formation permeability. The proposed test is made by injecting fluid at constant pressure, recording injection rate as a function of injection time. After one to four hours of injection, the well is shut in and fall-off of bottom-hole pressure is obtained as a function of shut-in time. Formation permeability is estimated by an iterative technique. First, a value of formation permeability is assumed. Then, a plot of the recorded injection rate as a function of dimensionless time is made, using the assumed pertneability value. From the slope of the injection-rate curve. a new value of formation permeability is calculated. If the new value agrees with the original assumed value, the assumption was the correct formation permeability. If the values do not agree, the process is repeated using the new permeability value in the calculation. Convergence is rapid, and a reliable permeability value results. Pressure fall-off data are used to check the result. Graphs of pressure and injection rate us functions of time given in the paper show that changes in permeability of the formation in the neighborhood of the wellbore are disclosed by this technique. Thus, the short-term test can he used to detect formation damage. Also, a rough measure of the radial extent of damage can be inferred, which is helpful in designing stimulation treatments. The mathematical model used for this work was a single-zone, horizontal reservoir with a damaged zone in which permeability decreased continuously as radial distance to the wellbore decreased. This model is more realistic than the usual two-zone, discontinuous permeability model used in published works; calculations indicate the realistic model is valid. Vertical variations in horizontal permeability were studied with this model, and results indicate that the permeability measured by the short-term test is the mean horizontal permeability for the vertical interval tested. The proposed short-term test thus should be useful in detecting and characterizing formation damage and in measuring formation permeability needed in calculating reservoir transmissibility. INTRODUCTION To plan the most efficient production or injection schedule for a well and to design or evaluate the optimal stimu- lation treatment, it is necessary to know the properties of the reservoir adjacent to the well, particularly the reservoir transmissibility and characteristics of a damaged zone, if one exists. Several techniques for determining reservoir transmissi-bility from well tests have been presented in the literature. 1,2,3,4 All these techniques rely on conducting constant-rate well tests that often are difficult to execute. A constant-pressure well test is generally easier to carry Out. and this paper contains the first available method for the analysis of constant-pressure well tests. Determination of wellbore damage from transient well tests has been the subject of several papers."" From these studies it is apparent that information necessary for determination of the characteristics of a damaged zone is available shortly after the transient well test is initiated. Consequently, it may not be necessary to carry out an extensive well test (for example, a pressure build-up test) if the primary purpose of the test is to detect the existence of wellbore damage. All previous studies of well testing to determine wellbore damage have been based on the two-zone perrneability model. In this model the damaged zone has a permeability k,, extending to a radius r,,, and the formation permeability k obtains from r, to the drainage radius r,.. Consequently, there is a discontinuity in permeability at r = r,,. This discontinuity can be eliminated by assuming a continuous variation in permeability through the damaged zone. The effect of this assumption on transient well tests is discussed in following sections of this paper. In addition, all formations have within them vertical permeability variations associated with lithology changes throughout the zone of interest. This paper also considers the effect of these variations on transient well tests. ANALYSIS OF CONSTANT-PRESSURE WELL TESTS The mathematical analysis associated with the injection of fluid at constant wellbore pressure into a single-zone, horizontal reservoir completely filled with a fluid of small and constant compressibility and constant viscosity is given in Appendix A. In this analysis it is assumed that the well is located at the center of an undamaged, circular drainage area. From this analysis, the formation permeability can be obtained as follows. 1, Estimate a value for the formation permeability k. 2. Prepare a plot of injection rate q vs

Jan 1, 1967

By H. K. Najarian

AT Josephtown, Pa., on the south hank of the Ohio River about thirty miles northwest of Pittsburgh, is the Josephtown electrothermic zinc smelter, which operates as a custom smelter receiving both domestic and foreign concentrates. Constructed in 1930, the plant was designed to produce zinc oxide and to process 124 tons per day of zinc concentrate obtained mainly from the Company's New York State mines. Zinc condensing equipment was developed in conjunction with the St. Joe electrothermic. furnace and commercial production of zinc metal started in 1936. Expansion of the plant and equipment during 1939 and 1940 brought the processing. capacity to upwards of 300 tons of concentrate per day; and the plant operated at peak capacity during the war years, earning the Army-Navy "E" award and three subsequent stars. A postwar plant expansion is now under way, designed to increase the capacity to 500 tons per day of concentrate, with an estimated daily production of 160 tons of zinc metal of various grades, about 100 tons of zinc oxide, and 425 tons of sulphuric acid as major products.

Jan 1, 1947

By RUSSELL C. FLEMING

GILSONITE is a brilliant black, tarry-like bitumen, classed technically with glance pitch and graharnite as an asphaltite. As found it is brittle, breaking much like ice, and has a conchoidal fracture. Purest forms are used in the manufacture of paints, varnishes, electrical irisulatiorl, and inks for rotogravure; molded articles such as switch handles, telephone mouthpieces, and but- tons are made from the intermediate grades, and the poorer grades are used for the saturation of felt. According to the U. S. Bureau of Mines figures, production grew from about 4000 tons mined in 1904 to 55,000 tons in 1929. This asphaltic substance is found only in the Uintah basin in northeastern Utah, in veins over a wide area. Veins in the vicinity of Fort nuchesne were first discovered about 18G2, on what was then the Uintah Indian reservation, and the vein matter was originally called Uintaite because of that fact, In the early days, S. H. Gilson. of Salt Lake City, was so persistent and zealous in his efforts to develop the deposits and find a market that the name gilsonite was given to the material. Later, the wider and more renowned wins near Wayson and Dragon, in extreme eastern Utah, became the main supply.

Jan 1, 1932

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

By Frank Marotta, Louis B. Lesem, Frank Greytok, John J. McKetta

Although one of the primary variables in the calculation of the flowing bottom-hole pressure in gas wells from surface measurements is the temperature at any point and its distribution in the flow-string, only few experimental data are available in the literature and little attention has been given to analysis of the problem. Virtually all of the recently published methods of calculating flowing bottom-hole pressures depend on the assumption that either the temperature is constant at some average value or that the variation is linear with depth. The purposes of this work are to analyze the problem theoretically and to verify the analysis by comparison with experimental data so that practical problems in the analysis of the behavior of gas wells can be solved with greater accuracy, reliability, and ease. MATHEMATICAL OUTLINE OF PROBLEM Assuming that: 1. The mass velocity and chemical composition of the gas stream are constant and in normal gas well operations, the change in linear velocity in the entire flow-string is trivial, 2. The product of the density and heat capacity of the gas is constant, 3. No horizontal temperature gradient exists in the gas stream, 4. Net flow of heat by conduction within the formation and in the gas stream in the vertical direction is trivial in magnitude and can be neglected, 5. The regional vertical geothermal gradient is constant, and 6. The temperature of the gas entering the borehole is constant, and equal to that of the reservoir, a set of two simultaneous, linear partial differential equations with appropriate boundary conditions was derived to describe the temperature distribution in the gas stream and the surrounding formation. These equations were solved by operational techniques for the distribution of temperature in the gas stream. The resulting integrals were evaluated numerically on an IBM 604 at the Machine Accounting Div. of the Railroad Commission of Texas. DERIVATION OF FUNCTIONS FOR THE DISTRIBUTION OF TEMPERATURE The physical system is a circular hole of radius a in an infinite medium with thermal conductivity K, density p8, and heat capacity c,. Under shut-in conditions the well is in thermal equilibrium with the surroundings and the increment in temperature is given by - ?T3/L x. Gas of density pg and heat capacity c.. flows upwardly through this hole in the direction of increasing x with a linear velocity W. Writing a heat balance on an element of gas ?x in thickness, convective heat transfer + conductive heat transfer + energy required to lift a unit mass of fluid = change in energy content. pa2W po Co To - pa2Wpo Co To x+xx - 2apK?x ?T8/?r r=a - Wpa2 po?x/778 = CoPopa2?x?To/?t... Dividing by (copopa2?x) and taking the limit as ?x tends to zero, -W (?To/?x + 1/778Co) + 2 K/a Po Co ?T3/?r r=u = ?To/?t

Jan 1, 1958

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By P. H. Turnock, R. D. Pehlke

The effects of mutual interactions between elements on the solubility of nitrogen in liquid iron alloys containing chrormium, columbium, molybdenurn, nickel, or silicon have been determined. The equilibrium nitrogen solubilities in the liquid iron alloys were measured by the Sieverts method. The second-order effects caused by the presence of chrormium, columbium , or silicon in the melt were found to be significant. The solubility of nitrogen in liquid iron alloys containing several alloying elements has also been measured as a function of melt temperature and nitrogen pressure. The heat of solution of nitrogen in microcomponent iron alloys has been found to be a function of the logarithnz of the activity coefficient of nitrogen, irrvespectilje of the composition of the melt. The heat of solution of nitrogen in pure liquid iron was determined to be 1265 ± 450 cal per g-atom of N over the temperatxue range 1600° to 1800°. Sieverts ' law was obeyed for all melt compositions studied in the pressure interval 0.4 to 1.0 atm. The solubility of nitrogen in liquid pure iron and in many dilute binary liquid-iron alloys has been the subject of many investigations. Pehlke and Elliott' made a comprehensive investigation on this subject in which they summarized and compared previous researches. However, the practical application of these solubility studies requires prediction of the nitrogen solubility in the multicomponent alloys encountered in operating practice. The interaction parameter as defined by wagner2 has been used to predict the behavior of a solute in a complex alloy, and a modification of this approach has met with reasonable success in several instances.'1"5 The necessity for extending the nitrogen solubility data on binary alloys is caused by the lack of direct measurements of the solubility of nitrogen in molten alloy steels. A direct comparison between measured solubilities and those predicted for multicomponent alloys based on data in binary systems has been made in only a few instances, and most of these were reviewed by Langenberg,6 who developed a graphical technique for predicting nitrogen solubilities in multicomponent iron alloys. The solubility of nitrogen has also been studied over the entire Fe-Cr-Ni ternary system by Humbert and Elliott.? Both studies compared the solubilities computed from binary iron alloy data with those measured in ternary alloys in the liquid state at 1600°C. Most of the nitrogen solubility measurements referred to above were for iron alloys at 1600°C; thus, the ability to predict nitrogen solubilities in molten iron alloys has been restricted primarily to alloys at 1600°C. Recently, Nelsson8 devised an approximate method for calculating the change in nitrogen solubility in molten iron alloys as a function of temperature, but an assumption of regular solution behavior limits the applicability of the method. Chipman and Corrigan9,10 have developed an empirical correlation. based on the activity coefficient of nitrogen in the iron alloy at 1600°C, which facilitates the estimation of nitrogen solubilities at higher temperatures. This method also has limitations, due to the necessity of calculating the activity coefficient for nitrogen in a multicomponent iron alloy at 1600°C from the nitrogen solubility data for binary iron alloys. The shortcoming of such a straightforward approach to the problem of predicting nitrogen solubilities is the disregard of mutual interactions between elements in a complex iron melt. This investigation was conducted in an attempt to provide a more reliable method of predicting nitrogen solubilities in multicomponent iron alloys. The effects of the mutual interactions between chromium, nickel, silicon, molybdenum, or columbium in iron were studied, using the Sieverts' technique1,7 to measure the effects of alloy composition, temperature, and pressure on the solubility of nitrogen in ternary liquid iron alloys.

Jan 1, 1967

By G. W. Nabor, A. S. Odeh

The effect of production history of a well on the results of two-rate flow tests, and conventional build-up analyses was investigated. The effect was examined by means of digital computers and an R-C network model, respectively, for wells with infinite and finite radii of drainage. For systems which behave as infinite, it was found that production history and the duration of production at constant rate prior to the initiation of the test have important effects on the results. During build-up time equal to about one-fourth of the stabilized time, correct permeability-thickness product calculations can be made. For wells with finite radii of drainage, the time was determined during which the straight line can be satisfactorily used for permeability-thickness product calculations in case of drawdowns and build-ups. On build-ups, the dimensionless time (based on the external radius) during which the straight line gives reliable results was detertriined to be about 1/12. This is one-fourth as long as that of the drawdown. The investigation was done theoretically, and subsequently was verified by R-C network model runs. General interpretive rules were formulated which, if not followed, could lead to serious errors. Moreover, a recommended testing procedure is reported. INTRODUCTION The method used by most reservoir engineers for estimating formation characteristics in a producing well is the analysis of pressure build-up data. The method originally devised by Horner' makes use of the point source solution to the diffusion equation. This solution is approximated by a logarithmic function and the superposition principle is employed to arrive at the well known pressure build-up equation:where q, the flow rate, is in reservoir B/D; ft is in cp; kh is in md-ft; At is the shut-in time; and t is the producing time. At and t are in any consistent time units. Ey. 1 is applicable to a well of unlimited drainage radius which produces at a constant rate q from zero to time t and is then shut in. Such a constant production rate seldom obtains in practice. Therefore. a correction term must be applied to Eq. I to account for the varying rate. Two theoretically accurate methods are available for treating the variable rate case. The first, originally derived by Horner,' is based on the application of the superposition theorem. It requires knowlege of production history of the well as a function of time and results in lengthy and laborious calculations. The second t*q* niethod is suited for short production tests and requires that the shut-in time be at least one and one-half times the production time. A third method which is not based on any theoretical justification and which was suggested by Horner as a "good working approximation" is the one used by the majority of reservoir analysts. especially when the well has been producing for a long time and the t*q* method is not practicable. The key to this method is in choosing or determining the t that appears in Eq. 1. Horner suggested using a corrected time t, in place of t. t, is calculated by dividing the total cumulative production by the last established rate. Therefore, a normal procedure of pressure build-up testing is to stabilize the well at a constant rate for at least 24 hours before shut in and to use the stabilized rate to calculate t,. The analysis is then made by plotting either or P. and examining the resulting plot for the expected straight line to calculate kh and the original reservoir pressure. Recently, Russell" proposed a method for determining formation characteristics from two-rate flow tests. His method reduces to pressure build-up if the second flow rate is zero. Russell uses the Horner simplified procedure for calculating a corrected t,. His method also requires the stabilization of the well at a constant rate q which is used to calculate t,. Theoretically, the above procedure is valid for a well with an unlimited radius of drainage or with a limited radius as long as the boundary effect has not been felt by the well. Several authors'' derived formulas which allow the estimation of time during which limited reservoirs behave as infinite ones and, thus, can be treated by unsteady-state mechanics. One equation derived by Swift and Kiel' terminates the application of unsteady-state theory when the drainage radius reaches one-half the reservoir radius. Thereafter, steady-state behavior obtains. Another equation derived by Jones'" initiates steady-state

Jan 1, 1967

By F. N. Flynn

- Introductory IN 1882, The Arizona Copper Co. Ltd., acquired producing copper mines at Metcalf and Morenci (locally called Longfellow). Metcalf is situated a distance of 7 miles, and Morenci a distance of 6 miles from the general office of the company at Clifton, Ariz. A reduction works with five blast furnaces was built in the center of the town of Clifton in 1884 and operated until January, 1914. Concentration of oxidized ores was begun in 1890-1891, in a mill built adjoining the smelter, and in October, 1893, a leaching process was started for treating tailings from the oxide mill. A sulphide concentrator with 300 tons capacity was built at Clifton and started treating chalcocite ores in July, 1896. This was the first mill to treat low-grade copper-sulphide ores successfully. Another concentration mill for sulphide ores was erected at Morenci in 1900. The, sulphide mills are now being remodeled to treat ores by concentration and flotation, with a capacity of 4,000 tons at Morenci and 500 tons at Clifton. The leaching plant has not been running since September, 1914. The average yearly production from this company's mines and reduction works from 1885 to date has been: Pounds 10 years ended 1894 6,864,902 10 years ended 1904 20,439,614 10 years ended 1914 : 32,665,905 Part of year 1915, to Sept. 12 30,206,106 4 months of 1916, to June 15,964,840 June, 1916...: ? 4,900,000 Construction on a new smelting plant was started in February, 1912, and finished in February, 1914. In the Transactions, vol. 49, E. Horton Jones published "Unit Construction Costs from the New Smelter of the Arizona Copper Co., Ltd:," which fully describes the construction of this plant, with details of costs.

Jan 9, 1916

By M. T. Simnad, G. Derge, Ling Yang

STUDY of diffusion in molten substances is important in at least two respects. Diffusion data, combined with thermodynamic and kinetic information, throw light on the structure of the liquid state. Moreover, a knowledge of diffusion coefficients and their temperature dependence is useful in ascertaining the controlling step in many metallurgical reactions. Although diffusion measurements have been made on a number of molten salts, slags, metals, and alloys,'-'" the results available are still limited and widely scattered, especially for the high temperature melts. It is the purpose of this investigation to establish reliable procedures for the measurement of self-diffusion coefficients in high temperature melts and to use these procedures to determine the self-diffusion coefficients of iron in molten Fe-C alloys of different carbon contents. Experimental Measurement of self-diffusion coefficients in high temperature melts is usually carried out by using one of two methods. In the first, diffusion takes place between two cylindrical samples of the same material, one of which is made radioactive. The diffusion coefficient is calculated from the radioactivity penetration curve in the solidified sample after the diffusion. In the second method, samples contained in capillaries of an inert substance are immersed in an infinite reservoir of the same material. Either the material in the capillary or that in the reservoir is made radioactive and the diffusion coefficient is calculated from the change of the radioactivity of the sample in the capillary after the diffusion. The second method is simpler because a radioactivity penetration curve is not needed for the calculation of the diffusion coefficient; however,.it is valid only when no convection has occurred in the capillary during the diffusion. A radioactivity penetration curve is therefore always useful in indicating that the required conditions for the diffusion are ful- filled. Towers and Chipman" recently studied the self-diffusion of calcium and silicon in CaO-Al,O,-SiO, melts by using the capillary method. Instead of measuring the change of the radioactivity of the sample in the capillary, they autoradiographed the sample after the diffusion and calculated the diffusion coefficient from the intensity distribution of the autoradiograph. Their method is useful when the radioactive isotopes are weak ß-emitters, but is very difficult, if not impossible, to apply to cases involving strong ß or y-emitters. For such cases, sectioning of the sample according to the method of Morgan and Kitchener' may be used for the construction of the radioactivity penetration curve. The self-diffusion of iron in molten Fe-C alloys has been studied in this manner and the experimental procedures are described as follows: The diffusion apparatus is shown schematically in Fig. 1. The bath consisted of about 200 g of an Fe-C

Jan 1, 1957

BRANCH COUNCILS MINING BRANCH R M Foose, Chairman (Industrial Minerals) Carroll A Garner (Coal) J V Beall, Eastern Secretary A B Cunmins (Industrial Minerals) R E O'Brien, Western Secretary E D Gardner (Mining, Geology, and Geophysics) Carroll F Hardy (Coal) Philip J Shenon (Mining, Geology, and Geophysics) R E Byler (Minerals Beneficiation) A C. Callen (Mineral Industry Education) Grover J Bolt (Minerals Beneficiation) R J Lund (Mineral Economics)

Jan 1, 1951

BRANCH COUNCILS MINING BRANCH R E Byler, '53, Chairman (Minerals Beneficiation) - C M. Cooley, Acting Secretary A Lee Barrett, '54, (Coal) Carroll A Garner, '53, (Coal) E. H Crabtree, '54, (Minerals Beneficiation) Ian Campbell, '54, (Industrial Minerals) A B. Cummins, '53, (Industrial Minerals) E. D Gardner, '53, (Mining, Geology, and Geophysics) LeRoy Scharon, '54, (Mining, Geology, and Geophysics) R. T Gallagher, (Mineral Industry Education) John H Ffolliott, (Mineral Economics)

Jan 1, 1952