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By Albert G. Zima

According to recently puhlished statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet. Drill Tools Modern rotary drilling tools are the product of ingenious design and careful selection and adaptation of materials used in their construction. They must withstand terrific abrasion and, because of their compactness, must be designed to resist exceedingly high unit stresses. In bits, core drills and reamers, the bodies are made of either forged or cast alloy steels, heat-treated to develop a combination of high strength and toughness. To provide sufficient strength to the threaded portions and to protect the threads from distortion or damage, the box or pin sections of the tools are hardened to approximately 310 to 330 Brine11 hardness number. Drill and reamer cutters are generally of the movable type; i.e., serrated cones, cylinders or disks, which can readily be replaced when

Jan 1, 1935

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark's papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By A. J. Phillips, C. G. Grant, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Wm. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By Albert G. Zima

According to recently puhlished statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet. Drill Tools Modern rotary drilling tools are the product of ingenious design and careful selection and adaptation of materials used in their construction. They must withstand terrific abrasion and, because of their compactness, must be designed to resist exceedingly high unit stresses. In bits, core drills and reamers, the bodies are made of either forged or cast alloy steels, heat-treated to develop a combination of high strength and toughness. To provide sufficient strength to the threaded portions and to protect the threads from distortion or damage, the box or pin sections of the tools are hardened to approximately 310 to 330 Brine11 hardness number. Drill and reamer cutters are generally of the movable type; i.e., serrated cones, cylinders or disks, which can readily be replaced when

Jan 1, 1935

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By F. H. Spedding

From thermal, metallographic, X-ray, dilatometric, and electrical resistance data a Phase diagram is proposed for the La-C system. TWO compounds are formed, body-centered-cubic Laz C, having a large range of solid solubility, and body -centered-tetrago-nal Lac2 . The former melts incongruently at 1415°C, and at 25OC it has an electrical resistivity about two and one-half times that of bure lanthanum. The latter melts congruently at 2356°C and at room temperature has an electrical resistivity about equal to that of bure lanthanum. The addition of carbon to La lowers the melting Point of La about 115' C, raises the higher (B-Y) transfomzation about 10" C and appears to have no effect on the lower ( a-0) transformation. The addition of carbon appears to lower the oxygen content in the metal and improve the machinability; however, the tendency to oxidize is increased. Two eutectics are formed in the system. The first occurs at 2.2 pct C and melts at 806" C, while the second occurs between Lac2 and C with a melting point of2271"C. PETTERSSON,~ in 1895, was the first to prepare lanthanum dicarbide by heating the oxide with carbon in an electric furnace. He showed that this yellow, crystalline but brittle carbide had a formula corresponding to LaCz and that it reacted with water with the evolution of hydrogen and hydrocarbons and the formation of the hydrated oxide. Von Stackelberg's investigation of the crystal structure of the MCz carbides showed that the lanthanum dicarbide is of the tetragonal calcium dicarbide-type structure. He found the lattice parameters were a = 3.92 and c = 6.56.* Bredig,' using X-ray methods, showed that the room-temperature form of lanthanum dicarbide is stable up to 1750 °C and that above this temperature it transformsoto a face-centered-cubic structure, a = 6.0 ± O.lA, probably of the pyrite, FeSzstruc- typ? The reported discovery of two new cerium carbides, suggested that a corresponding face-centered-cubic lanthanum monocarbide and a body-centered-cubic lanthanum sesquicarbide might exist. This paper describes work on the lanthanum-carbon system which is part of a study of the rare earth metals and their alloys now in progress in this laboratory. EXPERIMENTAL PROCEDURE Source of Materials—The lanthanum metal was prepared at the Ames Laboratory by metal1o;hermic reduction of the fluoride with calcium metal. The results of spectrographic and chemical analysis indicated the presence of 0.01 pct Y, Al, Cu, Fe, and Si; 0.02 pct Ca and Mg; 230 ppm C; and 115 ppm N. The carbon used was of two types: 1) "National Special Graphite Spectroscopic Electrodes," and

Jan 1, 1960

By Richard Paul Seelig

THE following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which may stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. EXPERIMENTAL APPROACH The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. In as much as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a compressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Al- though these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself,8 calls attention to the fact that the properties

Jan 1, 1947

By H. J. Rose, J. J. S. Sebastian

When coal is stored under ordinary conditions, progressive changes take place in its chemical and physical properties. These changes are largely caused by the reaction of atmospheric oxygen with the coal substance. Although this "oxidation" or "weathering" occurs slowly in the case of high-rank coals, it is nevertheless a matter of considerable importance, since even a small amount of oxidation may affect the value of coal for carbonization purposes. Coal storage is a necessity at all carbonizing plants. In normal times there are about 5,000,000 tons in storage at by-product coke ovens and gas retorts in the United States, as compared with an annual throughput of about 75,000,000 tons. In other words, the average coal reserve at such plants is slightly less than one month's supply. However, owing to the cost of storage and recovery, coal is usually left in stockpile for as long a time as the management thinks advisable. Storage for six to eight months is common practice and is, in fact, a necessity at certain plants which obtain their coal by water routes that are closed during winter months. Modern by-product coke ovens operate continuously, and they are not cooled down from the time that they arc put into operation until they are shut down for rebuilding—perhaps 20 years later. This continuous operation is imposed by silica-brick construction and high operating temperatures. It is therefore obvious that coke plants must at all times maintain an adequate supply of stored coal, in order to prevent a failure in supply from any cause whatever. Thus when strikes or other emergencies threaten, abnormally large coal stocks are accumulated and held at coke and gas plants. Many of these plants have been forced, at some time or other, to use coal that has been stored for several years. Such coal may fail to coke at all, or it may produce a dirty appearing, weak coke of reduced value. The yields of salable by-products may also be distinctly lowered. However, it must not be assumed that slight oxidation or heat effects are always injurious. Certain high-volatile coals produce a stronger, blockier

Jan 1, 1930

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By B. A. Kulp, R. R. Reeber

Lattice parameters for the wurtzite form of' CdS mere measured by powder X-ray diffraction techniques over the temperature range 26° to 1000 K'. A negative thermal -expansion coefficient was determined parallel and perpendicular to the c axis below 13.5°K. Near 808°K, the curves of the a, parameter, the differential thermal expansion, and the resistivitv vs absolute temperature exhibited a reversible discontinuity. j\. direct determination of the lattice parameters of CdS over an extended temperature range is of particular use in interpretation of the effects of high pressure on the band structure of semiconductor materials. For example, Langer' has studied the effects of pressure on the absorption edge of CdS from 77°K to room temperature. In order to properly interpret his results it is necessary to know the change in lattice constants as a function of temperature for the wurtzite, zincblende, and rocksalt2 modifications of this material. Thermal-expansion measurements for CdS, wurtzite phase, have previously been determined over a limited temperature range.s74'5 The zincblende phases, of other compounds with similar bonding, have been investigated by Novikova et a! .'' Previous thermal-expansion measurements for metals with hexagonal symmetry have for the most part used bulk sample techniques for low-temperature result. Most X-ray measurements at low temperature have been on materials with cubic symmetry.'jQ The use of X-ray powder-diffraction techniques offers a convenient and accurate method of measurement over a wide temperature range. The X-ray method, besides measuring unit cell size, also provides information about change in structure type and the nature of some of the stacking defects present. I) EXPERIMENTAL PROCEDURE The thermal expansion was measured by X-ray powder-diffraction techniques. Lattice parameters for the range 300" to 1000°K were determined in a 19-cm Unicam camera. From 26" to 300°K a 34-cm back-reflection camera with the Van Arkel" film arrangement was used. The sample was bonded to a copper cold finger below a helium, hydrogen, nitrogen, oxygen, dry ice, or ice brine bath in a metal cryistat. che inner bath was surrounded by another one for radiation shielding. Nitrogen was used in this outer bath for the very low-temperature runs while dry ice and acetone was used for the 195°K point. CuKa X-rays, filtered with a nickel foil, entered the cryostat through a 0.001-in.-thick aluminum window. During a typical 9-hr exposure the sample was continuously rotated through a 30-deg arc. Heat losses from the sample holder limited the minimum temperature attained to 26°K with helium in the inner dewar. Temperature calibration between 25" and 125°K was determined with an Allen Bradley 300-ohm carbon resistor. The resistor was attached to the back of the copper finger with a thin layer of silicone grease. Liquid He, HZ, N2, and O2 baths were used to calibrate the resistor. Temperature variation is estimated to be *2"K with a slightly higher uncertainty at room temperature and 264°K. The thermal expansion of high-purity germanium from 373" to 900°K was measured as a calibration for the Unicam camera. This value was compared with the known value1' for the thermal expansion. A discontinuity in the thermal-expansion coefficient of the CdS a, parameter was observed. Similar discontinuities in the resistivity and differential thermal analysis at the same absolute temperature indicate that the temperature error is *5°K in the temperature range above 500°K. Temperature errors in the Unicam camera below 500°K are appreciably higher due to large gradients in the resistance furnace. II) SAMPLE PREPARATION The CdS was Eagle Picher ultrapure grade. The crystallite size range of the as-received powder

Jan 1, 1965

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts' apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By N. J. Grant, B. C. Giessen, U. Wolff

With the aid of the splat-cooling technique of rapid quenching, metastable alloy phases based on antimony ad bismuth have been prepared. At room temperature, simple cubic phases were found in the Sb + Au, 56 + Yd, and Sb + Ni systems. Another phase was retained in the Au-Bi system at -190°C; in this systent, a microcrystalline phase and a rhombohedrally distorted phase were also observed. The crystal chemistry of these phases is discussed in terms of their valence electron concentration range. A remarkable five-step Phase sequence was found upon heating and equilibration of certain metastable Au-Bi alloys. USING the splat- cooling technique of rapid quenching from the liquid,' a large number of metastable intermediate alloy phases have been prepared in recent years. Thus, Hume-Rothery phases of the hexagonal type based on the valence electron concentration have been produced in systems where they are missing in equilibrium, e.g., Ag-Ge 1 or AU-Sb. 3 In a comprehensive study of metastable alloys based on tin, simple hexagonal metastable y phases were found, raising the total of stable and metastable y phases from 3 to 13. 4 In the In-Bi system, five new metastable intermediate phases were retained.' In most cases, the new metastable phases have some crystal chemical characteristics in common: a) They have rather simple, elementlike structures with few atoms per unit cell, e.g., y phase,4'5 or the metastable primitive cubic phases in the Ag-Te and and Au-Te systems.= b) Their structures are often related to those of the terminal phases, or to elements that are straddled in their position in the periodic table by the constituent elements; this is the case for metastable ß (In-Bi) with the structure of white ß Sn,' or metastable a (Cd-sn). 4 c) They seem to represent the crystal structures appropriate to certain average group number (AGN) ranges in which no or few single-phase structures exist in equilibrium. These average group number ranges can probably be equated in the case of many elements of the Ba(Zn)-Bs(As) groups with the averaged valence electron concentration. In the present work, the splat-cooling technique has been applied to the alloys of antimony and bismuth. In equilibrium, neither element forms intermediate alloy phases with other B elements from groups Bl(Cu) to B4(Si) that contain more than 66.7 at. pct of Sb or Bi, respectively, e.g., AUSb 2. 7 Thus, antimony- or bismuth-rich phases, which might be closely related to antimony or bismuth, and which would reflect struc- tural changes occurring on alloying with small amounts of addition elements, do not exist. Also, the terminal solubility of antimony and bismuth for all B metals is very small. It was therefore of interest to investigate the influence of enforced, nonequilibrium solid solution of addition elements in antimony and bismuth on their crystal structures. It was found that additions of group B 2-B4 metals act distinctly differently than additions of group T 10 and B1 metals. The latter set of additives will be treated here. EXPERIMENTAL TECHNIQUES Alloy preparation and splat-quenching followed closely the procedures described in Refs. 1, 4, and 5; they consisted of the preparation of master alloys from high-purity starting materials (99.99+ pct) and blast-atomizing of 20-mg quantities onto copper sheets. The resulting approximately 1 to 5 u thick foils were investigated by X-ray diffraction. The cooling rates obtained are of the order of 107 to 10 8 C per set,'" causing solidification to proceed at a rat; of approximately 100 cm per sec.' Powder patterns of the resulting fine-crystalline materials were taken with filtered CuK, radiation. For antimony alloys the substrates were held at room temperature and for bismuth alloys at -190°C both during splat foil deposition and X-ray investigation. Annealing treatments at several

Jan 1, 1969

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.' The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961