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By W. R. Hibbard

THE classical work on the electrical conductivity of alloys was carried out by Matthiessen and his coworkers1 in the early 1860's. He attempted to correlate the electrical conductivity of alloys with their constitution diagrams, but the information regarding the latter was too meager for success. Guertler2 reworked Matthiessen's and other conductivity data in 1906 on the basis of volume composition (an application of Le Chatelier's principle with implications as to temperature and pressure effects), and obtained the following relationships between specific conductivity and phase diagrams (plotted as volume compositions) : 1—For two-phase regions, electrical conductivity can be considered as a linear function of volume composition, following the law of mixtures. 2—For solid solutions, except intermetallic compounds, the electrical conductivity is lowered by solute additions first very extensively and later more gradually, such that a minimum occurs in systems with complete solid solubility. This minimum forms from a catenary type of curve. Intermetallic compound formation with variable compound composition results in a maximum conductivity at the stoi-chiometric composition. Landauer" has recently considered the resistivity of binary metallic two-phase mixtures on the basis of randomly distributed spherical-shaped regions of two phases having different conductivities. His derivation predicts deviations from the law of mixtures which fit measurements on alloys of 6 systems out of 13 considered. Volency (Ionic Charge) Perhaps the first comprehensive discussion of the electrical resistivity of dilute solid-solution alloys was presented by Norbury' in 1921. He collected sufficient data to show that the change in resistance caused by 1 atomic pct binary solute additions is periodic* in character. The difference between the period and/or the group of the solvent and solute elements could be correlated with the increase in resistance. Linde5-7 determined the electrical resistivity (p) of solid solutions containing up to about 4 atomic pct of various solutes in copper, silver, and gold at several temperatures. He reported that the extrapolated"" increase in resistance per atomic percent addition is a function of the square of the difference in group number of the solute and solvent as follows: ?p= a + K(N-Ng)2 where a and K are empirical constants and N and Ng are group numbers of the constituents. This empirical relation was subsequently rationalized theoretically by Mott,8 who showed that the scattering of conduction electrons is proportional to the square of the scattering charge at lattice sites. Thus, the change in resistance of dilute alloys is propor-t,ional to the square of the difference between the ionic charge (or valence) of the solvent and solute when other factors are neglected. Mott's difficulty in evaluating the volume of the lattice near each atom site where the valency electrons tend to segre-gate: limited his calculations to proportionality relations. Recently, Robinson and Dorn" reconfirmed this relationship for dilute aluminum solid-solution alloys at 20°C, using an effective charge of 2.5 for aluminum. In terms of valence, Linde's equation becomes ?P= {K2 + K1 (Z8 -Za)2} A where K1 and K2 are coefficients, A is atomic percent solute, Z, is valence of solvent, and Zß, is valence of solute. Plots of these data for copper, silver, gold, and aluminum alloys are shown in Fig. 1. The values of K1 and K2 are constant for a given chemical period (P), but vary from period to period. The value of K, increases irregularly with increasing difference between the period of the solvent and solute element (AP), being zero when AP is zero. The value of K, appears to have no obvious periodic relationship. All factors other than valence that affect resistivity are gathered in these coefficients. Because of the nature of the coefficients, Eq. 1 is of limited use in estimating the effects of solute additions on resistivity unless a large amount of experimental data are already available on the systems involved. It is the purpose of the first part of this report to investigate the factors that may be included in the coefficients of Linde's equation. On this basis, it is hoped that the relative effects of solute additions on resistivity can be better estimated from basic data, leading to a more convenient alloy design procedure. It is well 10,11 that phenomena that decrease the perfection of the periodic field in an atomic lattice, such as the introduction of a solute atom or strain due to deformation, will also increase the electrical resistivity. Thus, in an effort to relate changes in electrical resistivity to alloy composition, it appears appropriate to consider the atomic characteristics related to solution and strain hardening

Jan 1, 1955

By Pervez Patel, Martin G. Frohberg, Demetrios Papamantellos

Model experiments were carried out on the mass transfer of iodine between n-hexane and a 4 2 X 10-3 M aqueous sodium hydroxide solution. The influence of mechanical stirring by means of small gas bubbles (ca. 0.01 ml in volume) on mass transfer was examined in independent experiments. The results were described with the help of the penetration theory and in the case of bubble stirring with the help of a mathematical model based on this theory. S LAG-METAL reactions, especially those in steel-making processes, often occur under conditions where gas is evolved in the form of bubbles that break through the slag-metal interface. It is known that stirring by means of bubbles increases the mass transfer coefficient, but there has been very little quantitative work done in this field. Because of the difficulties that attach to experimental work at high temperatures this study was confined to model experiments at room temperature. EXPERIMENTAL APPARATUS The transport of iodine from an n-hexane layer into a weak sodium hydroxide solution was studied a) with stirring by means of bubbles and b) with mechanical stirring. The apparatus for the experiments with bubbles consisted of the cell, two Dreschel bottles filled with hexane in order to saturate the nitrogen flow, one flow meter, and a nitrogen gas cylinder fitted with a fine-regulating valve. Fig. 1 shows the cell consisting of a glass cylinder 33 cm in height with an overall diameter of 7.5 cm embedded in a copper flange. The flange is connected to a Plexiglas plate and to the gas inlet. The Plexiglas plate has holes of 0.2 mm diam bored into it which are spaced 1 cm from each other. For the experiments with mechanical stirring the bottom of the cell was sealed off by a Plexiglas plate. The upper layer was stirred by means of a glass stir-rer and the bottom layer with the help of a magnetic stirrer in a counter rotatory direction. Both stirrer speeds could be varied continuously. EXPERIMENTAL PROCEDURE Iodine dissolves in n-hexane producing a stable violet color thus enabling the iodine concentration in

Jan 1, 1970

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homogeneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity p1 and a lower layer, extending to infinity, of resistivity pz. It has been shown by Lancaster-Jones2 that the apparent resistivity obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the formhere pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 — p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between pa/p1, h/a and k. Such a set of curves for the case when p1 > p2 is given in Fig. 1. When pl is less than pz it is more convenient to use conductivity instead of resistivity. Hence, if oa = the apparent conductivity = lip, and a1 = the conductivity of the upper layer = l/pl, it follows that GeophyGical prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" I1 and I2. The current of intensity J, supplied by this battery, passes through the earth between these elcc- trodes. A potential difference U will be measured between two other electrodes V1 and Vz, called "potential electrodes." According to the configuration of electrodes (Fig. I), the resistivity of a homogeneous soil results from the formula

Jan 1, 1940

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homogeneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity p1 and a lower layer, extending to infinity, of resistivity pz. It has been shown by Lancaster-Jones2 that the apparent resistivity obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the formhere pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 — p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between pa/p1, h/a and k. Such a set of curves for the case when p1 > p2 is given in Fig. 1. When pl is less than pz it is more convenient to use conductivity instead of resistivity. Hence, if oa = the apparent conductivity = lip, and a1 = the conductivity of the upper layer = l/pl, it follows that GeophyGical prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" I1 and I2. The current of intensity J, supplied by this battery, passes through the earth between these elcc- trodes. A potential difference U will be measured between two other electrodes V1 and Vz, called "potential electrodes." According to the configuration of electrodes (Fig. I), the resistivity of a homogeneous soil results from the formula

Jan 1, 1940

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;' Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of' the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.' In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By J. E. Neal, C. T. Naber, O&apos

Silicon thin films were deposited by electron beam evaporation in an ultrahigh vacuum onto (0001) and (1102) sapphire substrates. Attempts were made to correlate the structural properties of the deposited silicon films with the following: 1) substrate orientation, 2) substrate surface condition, 3) substrate temperature, and 4) deposition rate. The substrate temperatures were varied between 500° and 1000°C and the deposition rates were varied between approximately 50 and 700A per min. The following sapphire surface treatments were investigated: 1) annealing in the ultrahigh vacuum at 1200° C; 2) heating in a hydrogen atmosphere at about 1350°C; and 3) etching with silicon by evaporating silicon onto sapphire substrates heated to 1200° or 1300°C. Twinned silicon films were occasionally formed at substrate temperatures between the 800° and 1000°C on unprocessed mechanically polished substrates; however, the reproducibility and crystallinity of these films were generally poor. Single-crystal and twinned silicon films were formed at substrate temperatures between 700° and 1000°C on substrates which were silicon-etched at 1300°C prior to deposition. Fiber texture films were formed at substrate temperatures between 500° and 700°C. The (111) lattice plane of the silicon single-crystal films was parallel to the (0001) sapphire plane and the (100) silicon plane was parallel to the (1102) sapphire plane. TECHNIQUES are well-established for growing single-crystal silicon thin films on sapphire by chemical methods.'-* Vacuum epitaxial techniques have a number of advantages over chemical epitaxial techniques in the fabrication of thin film microcircuits.5 One of the most significant is that vacuum techniques are compatible with well-established procedures for forming vacuum-deposited thin-film resistors, capacitors, and interconnections. Salatna, Tucker, and young6 recently reported the formation of relatively poor crystalline-quality silicon films on sapphire by electron beam evaporation in a vacuum of about 7 x 10-7 Torr. The purpose of the investigation described here is to determine the relationships between the structural properties of silicon thin films deposited on sapphire substrates by electron beam evaporation in an ultra-high vacuum and the following: 1) substrate orientation; 2) substrate surface condition; 3) substrate temperature; and 4) deposition rate. The substrate temperatures were varied between 500° and 1000° C and the deposition rates were varied between approximately 50 and 700A per min. Two orientations of sapphire were used: (0001) and (1102). The thick-nesses of the films were between 8000 and 16,000A. The morphology and crystallinity of the deposited films and substrate surfaces were investigated by optical microscopy, electron microscopy, and electron diffraction. APPARATUS AND PROCEDURE A cross section of the ultrahigh-vacuum thin-film evaporator is shown in Fig. 1. The bell jar is stainless steel and copper gaskets are utilized at all seals. High vacuum is attained by a 6001iter per sec ion pump and a titanium sublimation pump. Sorption pumps are used to rough the system to a pressure of about 10 µ prior to starting the ion pump. Vacuums in the 10- 10 Torr range were attained after baking the system at about 250°C for 8 hr. Vacuums in the 10-8 to 10-9 Torr range were maintained during silicon evaporation. The silicon charges, which were cut from p-type single-crystal boules which had resistivities between 2000 and 4500 ohm-cm, were placed in the water-cooled copper crucible of a 180 deg bent-beam 5-kw electron beam evaporator. During evaporation, a molten zone was formed in the top center of the silicon charge, and the portion of the silicon charge in contact with the water-cooled crucible remained solid. The substrate heater, which has been described

Jan 1, 1969

By J. M. McCormack, R. K. Saxer, J. R. Myers

ThE Knudsen effusion technique was used to determine the chemical activities of copper and platinum in binary Cu-Pt alloys in the temperature range 1542" to 1673°K. Wiebke and Matthes1 previously obtained chemical activities of copper and platinum in this system at 673° and 923°K by the electromotive-force measurement method. They reported that the copper activities exhibited negative deviation from Raoult's law at all compositions. The chemical activities of platinum were found to change from a positive to a negative deviation at 923°K. Myles2 recently studied this system in the temperature range 1265° to 1356°K by means of the torsional-effusion technique. His results indicated that both copper and platinum exhibited negative deviation from ideality at all compositions. The use of the Knudsen effusion technique to obtain the vapor pressure of metals and alloys is well-known.3 In this work, Knudsen cells were fabricated from seamless tantalum tubing of 1-in. OD and 0.020-in. wall thickness; cell bases and covers were cut from 0.010-in.-thick tantalum sheet and welded to the cells in an argon atmosphere. Orifices were drilled and reamed to approximate a knife-edge of 30-deg included angle. Calculation based on Balson's4 derivation showed the orifice to be nearly ideal. All temperature measurements were made with a Leeds and Northrup disappearing-filament-type optical pyrometer at the orifice of the cell, which closely approximated black-body conditions and eliminated the need for emissivity corrections. Details of the experimental techniques used, and the necessary correction factors required during this investigation are essentially those previously described.5,6 Before investigating the Cu-Pt alloys, vapor-pressure measurements were obtained over specimens of pure (OFHC) copper. The pure-copper data5 served to assure the accuracy of the experimental apparatus and technique.

Jan 1, 1967

CONTENTS RUSSIA-R. C.-BECKSTROM 3 VENEZUELA-F. H. KAY 9 TRINIDAD-W. J. MlLLARD 20 RUMANIA-1. I. GARDESCU 26

Jan 1, 1932

By D. W. Fuerstenau

THE object of this article is to point out the experimental relationship which exists among contact angle, adsorption density, zeta potential, and flotation rate data. In each of the experiments discussed in this article, the surface properties of quartz, as a function of pH, were measured in solutions to which constant quantities of dodecylam-monium acetate were added. Morrow1 and deBruyn2 worked with solutions containing 4.08x10-5 moles per liter, whereas Fuerstenau3 and Seele worked with solutions containing exactly 4x105 moles per liter, but this difference is not significant. The pH of the solutions was regulated with HCI or NaOH in all cases. In each case, the addition of collector was constant, but the concentration of dodecylammonium ions decreased because of the formation of dodecylamine at higher pH values.2 Contact Angles: Gaudin and Morrow1 presented data for the contact angle of quartz in solutions containing 4.08x10-5 moles of dodecylammonium acetate per liter between pH 2 and pH 10.15. Using the same captive bubble techniques, the writer measured contact angles on quartz in solutions containing 4x105 moles of dodecylammonium acetate per liter at pH values ranging from 9.9 to 13.2. Both sets of data are presented in Fig. 1, in which the contact angle in degrees is plotted as a function of the pH of the solution. From pH 2 to about 8, the contact angle

Jan 1, 1958

By V. I. Purcell, S. C. Sun. R. E. Snow

A study including effects of 7) pH value, 2) fatty acid collector, 3) fuel oil, 4) interfering ion, 5) particle size, and 6) operational variables. Test results indicate feasibility of fatty acid flotation under certain restrictive conditions. FATTY acids have been used as standard collectors for floating the matrix1-8 but not the leached zone phosphate ores. After a series of investigations, Davenport9 and Tarbutton10 concluded that the Florida leached zone ores tested were unamenable to fatty acid flotation and must be upgraded by floating the siliceous gangue with Armac-T as collector. The cationic flotation was estimated11 to cost almost ten times as much as a fatty acid process that would ideally give the same flotation grades and recoveries of phosphates. Mineralization: Extensive deposits of leached zone aluminiferous phosphate occur in Florida."= The ore sample used for this work was obtained from the Virginia-Carolina Chemical Corp., Clear Springs area, Florida. The ore is a potential source of uranium and aluminum as well as phosphorus. Since the uranium and the recoverable aluminum are contained in some of the phosphate minerals, an upgrading of phosphate results in a corresponding enrichment of both uranium and aluminum. The phosphate minerals in the ore are primarily pseudo-wavellite, millisite, and carbonate fluorapatite, with a minor amount of wavellite. Quartz and clay are the common gangue minerals, quartz being predominant. Others present in small amounts are ilmenite, hydrated iron oxides, staurolite, monazite, and zircon. Experimental Procedures: After being dried to less than 1 pct surface moisture the material was dry-ground in a Hardinge conical ball mill to —6 mesh. The ground product was classified into 6/20, 20/200, and —200 mesh size fractions. On the basis of Table I, the coarse and fine size fractions were considered as phosphate concentrates, because of their high phosphorus contents. In contrast, the 20/200 mesh fraction, which was low in phosphorus, was used as the flotation feed. All the flotation tests, unless otherwise stated, were performed in a laboratory Fagergren machine under the following conditions: 1) 400 g of solid feed for each test, 2) 2000 rpm impeller speed, 3) 8.9 pH and 4-min conditioning, and 4) 3-min flotation. The procedure used for the quantitative bubble pick-up tests has been described previously.18

Jan 1, 1958

Jan 1, 1967

Jan 1, 1967

By Michael Hoch, Walter C. Wyder

The Cr-Ni system was investigated between 900" and 1400°C and 45 to 100 wt pct Cr. The Cr-Fe system was studied between 1200" and 1385°C and 70 to 100 wt pct Cr. Powdered alloy compacts were produced from high-purity chromium, nickel, and iron poulders. The compacts were sintered in an argon atmosphere and then machined into small, 0.030-in. diam cylindrical specimens. These were then heated by induction in the high-temperature X-ray diJfractwn camem under a helium atmosphere and irradiated with copper Ka radiation. From the results of the high-temperature X-ray diffraction patterns it can be concluded that chromium exists only in the bcc form, and that no eutectoid reaction occurs in the Cr-Ni system in the temperature interval 900" to 1400°C. The X-ray diffraction patterns are in agreement with the Cr-Ni phase diagram of Bechtoldt and Vacher, and Williams. It is possible that chromium undergoes one or more allotropic transformations between room temperature and its melting point. Most of the evidence was gathered from the study of the chromium-rich ends of the Cr-Ni and Cr-Fe binary systems. All the investigations rely heavily on indirect methods: thermal analysis, electrical resistivity, and micro-graphic inspection of quenched samples. In the present work the chromium-rich side of the Cr-Ni and Cr-Fe binary systems is studied, using high-temperature X-ray diffraction techniques. Thus the coexistent structures can be observed directly at temperature. PREVIOUS INVESTIGATIONS ~ansenl shows two possible Cr-Ni phase diagrams 1) a simple eutectic [Liquid =a-Cr(bcc) + y-Ni(fcc)], 2) a eutectic [Liquid+ P-Cr(fcc) + y-Ni(fcc)] and euctectoid [p-Cr(fcc) ==a-Cr(bcc) + yNi(fcc)]. The latter is based on the work of Grant and co-workers.2 Stein and rant'" placed the eutectoid composition at 1215°C and 68 wt pct Cr; their diagram is shown in Fig. l. Similarly, Sully3 also discusses the two proposed diagrams. Price and Grant,4 working on an isothermal section of the Cr-Ni- Fe ternary diagram at 1300°C, made no mention of a ß-chromium phase (fcc). The ß-chromium structure was also reported by Misencik 5 in the Cr-Nb(Cb) system. Williams 6 studied the Cr-Ni system using precipitation techniques. His work included the chromium and nickel solvus lines below 1250°C. He reported no ß structure nor any eutectoid reaction. The solvus lines which he produced were very similar to those of Jette, et al 7 below 1000°C. He concluded that Grant and coworkers2 had misinterpreted their data, and that effects which they had reported were actually due to the rapid and extensive precipitation of the nickel-rich phase. Bechtoldt and vacher8 used sintered powdered alloy compacts in an attempt to find the ß phase. They used metallographic and room-temperature X-ray diffraction techniques and also failed to detect the fcc chromium phase. They attributed the low slope of the chromium solvus at approximately 1150°C as the probable cause of the abundant precipitation obtained. They also stated that the precipitation was the probable cause for the abrupt discontinuities in the thermal analysis and electrical resistivity data which led to the conclusion that a eutectoid reaction existed. Fig. 1 also shows their diagram. Grigor'ev and coworkers9 investigated the polymorphic changes of chromium in the Cr-Ni phase diagram. Using standard microstructural and thermal analysis techniques, they published a phase diagram which contained five polymorphic forms of pure chromium and four eutectoid reactions. They stated that the room-temperature bcc chromium transformed to a fcc structure at 930°C, to bcc at 1300°C, to hcp at 1650oC, and then finally to bcc at 1830°C. The eutectoid reactions were placed at 850°, 960o, 1140°, and 1220°C. Also to be noted was the fact that the uppermost phase, the bcc above 1830°C, was different from the upper phase of Grant and coworkers,2 the fcc above 1840°C. Their eutectoid reactions, temperatures and compositions fall

Jan 1, 1963

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By Stuart St. Clair

In view of the great interest shown in the oil possibilities of Kentucky, one is impressed with the paucity of reliable literature on the oil fields of the state. A few brief reports by the Federal and State Geological Surveys are about the only reliable data available. When the estimated production figures, for 1918, are published by the U. S. Geological Survey, they will show a revival of the oil industry in the Blue Grass State during the past half decade. There will also be an increase in the production for 1919 and 1920, at least. Although as an oil-producing state Kentucky is small, compared with some of the other oil states, the present production and the area of undrilled proved territory is large enough to classify it as one of the important oil states of the Union. This paper will be confined to the Irvine District and the immediately adjoining areas which have been prospected with varying success. The Corniferous limestone or Irvine sand is the oil-producing formation in the area discussed. In my divisional nomenclature, the Irvine District includes the Irvine field, which extends from the town of Irvine eastward toward Campton; the Big Sinking area, which joins and lies to the south of the eastern part of the Irvine field; the Beattyville area, which lies to the north and northeast of the town of that name and joins the Big Sinking area; and the Ross Creek pool, which lies to the southwest of the big production and across the Kentucky River. Except for the Ross Creek pool, the main producing area is bounded on the east by the L. & E. R. R. and on the west and south by the Irvine Branch of the L. & N. R. R. Winchester and Lexington form the gateways and Torrent on the east, Irvine on the west, and Beattyville on the south are the principle entrances to the main fields. Evelyn, on the L. & N. R. R., south of Irvine, is the point of entrance to the Ross Creek area. Geology The geology of the Irvine District is very simple. The rock formations with which the oil man should acquaint himself lie between the lower measures of the Pennsylvanian sandstones and shales and the Devonian or Corniferous limestone, or Irvine formation. Only a very brief description of these formations will be given, as they have been described fully by E. W. Shaw.'

Jan 1, 1921

K. Baumgarten has returned from active service in France. He reports that he saw C. W. Campbell, formerly with the 2d Engineers on the Chateau Thierry front, and believes that the latter returned to the United States on August 1. He also saw J. J. Croston; G. J. Sielaff, recently transferred to the Gas Service; Thomas M. Smither, survivor of the Tuscania after a 10-mile swim to Ireland. While in Paris he en-deavored to see Prof. Sauveur, but was unsuccessful. F. K. Borrow was given a commission as Lieutenant in the Royal Garrison Artillery in 1914, but had to relinquish it, on account of ill health, in August, 1915. His health has much improved and he hopes to resume active work toward the end of this year. Davis, A. W:, see British Columbia Engineers, below. Alfred Fox, Jr., enlisted in the Public Schools Brigade, Royal Fusiliers, in September, 1914; was gazetted Lieutenant in the Royal Field Artillery in December, 1914, promoted to Captain in November, 1915, and Adjutant to 78th Brigade, Royal Field Artillery, in January, 1916. He was appointed Staff Captain of the 12th Divisional Artillery in November, 1917. He has served continuously in France since July 1, 1915. He was awarded the Military Cross in January, 1917, and four times mentioned in despatches. E. Fraser-Campbell writes that he joined the London University 0. T. C. in January, 1918, for five weeks; enlisted with the Argyll and Sutherland Highlanders in February, 1918, and attended a training course for officer cadets at Chatham for six weeks. He was commissioned 2d Lieutenant, Royal Engineers, in April, 1918. After two months on home training at Chatham, he landed in France on June 23, 1918, posted to 180th Tunnelling Co., R. E., and is now with his unit up on the line.

Jan 10, 1918

By B. K. Larkin

Solutions to the diffusion equation for a line source located anywhere in a region bounded by a circular discontinuity are presented. Such solutions follow automatically from the Green&apos;s function presented by Jaeger.4 Petroleum industry applications of this problem would include transient compressible fluid flow in porous media bounded by a discontinuity. Since several recent papers have treated the subject in less general form, it would appear that many workers in this area of the petroleum industry are not aware of Jaeger&apos;s work. STATEMENT OF THE PROBLEM In several trearments1,2,3 of the transient flow of compressible fluids in porous media it was convenient to consider a region to be bounded by a circular discontinuity. In such a region (Fig. I), the properties in Region 1, r < a, are constant but different from the properties in Region 2, r > a. Hurst, l using the Laplace transform, obtained solutions for a line source located in the center of such a porous medium. The purpose of this work is to point out that a much earlier paper by Jaeger4 presents the solution for a line source located anywhere inside the discontinuity. The assumption is made that a line source may be used to approximate a well. In the following material it is convenient to use the terms source and well as being equivalent; however, the reader should remember the distinction in applications. SOLUTIONS Jaeger presented the Green&apos;s function for a line source, or well, in the composite region shown in Fig. 1. In the most general form, the solution for a system of j wells in Region 1, each producing at a time varying rate, qi (t), is

By Charles R. Fettke

The permeability of an oil or gas sand is its capacity for transmitting fluids, either liquids or gases, under pressure. The permeability of a sand depends upon the size and shape of the openings in it and the extent to which these communicate with one another, as well as upon the ratio of their volume to the total volume of the sand. The apparatus employed and the method of procedure used by the authors in conducting the permeability tests have been described in a previous pub1ication.l For the tests described here 1/2-in. cubes were used. They were set in the lower end of a 1-in. union, inserted in a square hole cut in a hard rubber stopper which fitted into the lower end of the union. In the tests with air, volumes were measured with a wet American gas meter of 100 cu. ft. capacity. In those with water, distilled water at room temperature was employed, unless otherwise noted. DescRiption of Sands Tested The tests described in this paper were performed upon 18 samples representing typical oil and gas sands from 7 localities in northwestern Pennsylvania. For purposes of identification, the cores from which the samples came have been designated by capital letters, the sequence of the samples in the cores by numerals, and the individual cubes by small letters. All cubes from the same samples came from adjacent portions parallel to the bedding. Core A of the Bradford sand came from the north central part of the Bradford field, from an area where water-flooding operations have proved highly successful. Core B of the same sand was obtained from the southern part of the field. This core contained a so-called "loose streak," 7.5 ft. thick, in the middle portion of which B2 is a representative sample. The "loose streak" has given trouble in water-flooding but responded favorably to an air-drive, using a pressure of 300 lb. The natural production was increased approximately five times over a period of three years in which the air-drive was in operation. Core C, also of the Brad-

Jan 1, 1931

J. L. McK. YARDLEY,* Pittsburgh, Pa. (written dlscussion ?) .-It is interesting to observe how closely Mr. Hansen agrees with other investigators to the effect that the art of electrolytic zinc has left the realm of mystery. In his introduction, lie has said practically what Thomas French said in his paper "The Future of Electrolytic Zinc. "1 The successful electrolysis of zinc from sulphate solutions has not been an easy matter, and it is only within recent years that the difficult problem of depositing high-grade zinc has been satisfactorily: accomplished on a commercial basis. The principal requisite is. that the electrolyte shall be quite free from certain impurities. The methods by which freedom from these impurities is assured are now very well understood, and with experienced superintendents there is little difficulty in obtaining a high efficiency in that part of the process. When certain underlying principles are recognized, the difficulty encountered in dealing with the filtration of the acid and slimy solutions also largely disappears, although it has been a very serious one to the uninitiated. In the dissolving of the zinc from the roasted ore, there is nothing which any competent chemical&apos; engineer cannot undertake, and any other operations connected with the electrolytic process are either of little or no difficulty, or are common to the retort process. Mr. Hansen also agrees with R. G. Hall&apos;s statement in " Some Economic Factors in the Production of Electrolytic Zinc:"2

Jan 10, 1918