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By R. G. Mallon, R. L. Braun

Primary copper-sulfide ore deposits that are well below the water table can be chemically mined by in-situ high-pressure leaching. The leaching is accomplished by pumping oxygen gas into the bottom of a large underground flooded column of rubblized ore. Part of the injected oxygen dissolves under the high hydrostatic pressure in the column. With a high enough injection rate, the excess oxygen gas induces a convective circulation of oxygenated solution within the rubble column, which transports dissolved oxygen throughout the system. At elevated temperatures, this results in a relatively rapid dissolution of the copper minerals. A method of calculating the leaching rates is presented. The calculation is done by means of a finite-difference computer code that couples all of the processes relating to copper leaching, convective circulation, and the injection, dissolution, and consumption of oxygen. Results of the calculation for a typical case show that over 70% of the copper can be extracted in less than six years with good efficiency in oxygen utilization.

Jan 1, 1976

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By W. G. Moffatt, J. Wulff

BRAZED joints and their strength have for some time been of great practical as well as theoretical interest. A good summary of the previous work in this field may be found in the reports of the Armour Research Foundation. In spite of excessive scatter in test data, the fact that the strength of a brazed joint may exceed the ultimate strength of the brazing material itself by many times continues to be of interest and of value in engineering. That this is qualitatively due to plastic constraint of the brazing material by the faying surfaces of the base metal is not in dispute, yet no complete interpretation of the data exists. The purpose of the present work is not to provide such a new interpretation, but to report new experimental data which we hope may lead to a better understanding of the important variables concerned. The work of Bredz' definitely shows that the thinner a brazed joint is, the greater is its strength. Dianeter of a joint has seldom been taken into

Jan 1, 1958

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By Luis E. Vallejo

Experimental and theoretical analyses are presented to study the mechanics of growth and interaction for three inclined left-stepping, three inclined right-stepping and two inclined non-stepping cracks in a brittle material subjected to uniaxial compression. It was found that the non-stepping cracks did not interact and they propagated individually in a direction parallel to the uniaxial compressive stress. The propagating cracks formed in regions where tensile stresses developed. The left-stepping cracks interacted and formed branching cracks as a result of failure in tension of the material between them. Also, they propagated from their tips in a direction parallel to the uniaxial compressive stress. The right stepping cracks did not interact, but extended themselves from their tips following a direction parallel to the uniaxial compressive stress. The extended cracks formed in areas of compressive stresses.

Jan 1, 1984

By Niles E. Grosvenor

Complex underground mining problems are increasing as mining depths increase. Many of these problems have been solved mainly by unsystematized trial-and-error methods based on individual experiences. This system of solving mining problems has resulted in over-cautiousness whereby a large quantity of our mineral resources are left in the ground, or not enough caution with a resultant failure of the underground opening. From studies made of physical properties of rocks, large volumes of data have been collected as a source of finding correlation among the different physical tests or among certain rock types. Most of these studies have not produced satisfactory results because the investigator usually arrives at the conclusion that the results are too scattered to be reliable. The reasons usually given as the cause of this scatter are that rocks are nonhomogenous and non-isotropic. Similar types of poor correlation that were being obtained from compression tests in the Colorado School of Mines Mining Research Laboratory led to an investigation of a good method of making a simple unidirectional compressive strength test.

Jan 1, 1963

For some years MINING ENGINEERING has published abstracts of the articles appearing in each issue and also of the Transactions papers published in the Quarterly. Beginning this month, a list of key words is being given with each abstract as an aid to indexing the articles for ease in retrieving them when they are needed. The value of a home or office system of indexing and retrieving technical articles is hard to over-estimate. How often is it that a technical problem comes up and someone says: "Oh yes, I've read something about that." Many hours can be expended tracing down that nebulous source. A modest indexing and retrieval system will save those tedious hours, and the person who is able to produce technical documents when they are needed will achieve an enviable status for being on the ball.

Jan 1, 1964

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram for the gadolinium-cobalt system has been determined. Seven intermetallic compounds have been found at compositions corresponding to the follwing gadolinium-cobalt ratios: 3:1, 1:1, 2:3, 1:2, 1:3, 1:4, 1:5. The GdCor compound has a congruent melting point above 1600°C. whereas the remaining compounds melt incongruently. Eutectics exist at 16 wt pct Co and 84 wt pct Co, with melting points of 620° and 1260°C, respectively. PREVIOUS papers'" have recorded constitutional data for systems of gadolinium with iron and nickel. This paper presents data obtained on alloys of gadolinium with the remaining 3d transition element-cobalt. voge13 found that cerium forms, with cobalt, the intermetallic compounds; Ce3Co, CeCo, CeCo2, CeCo3, CeCo4, and CeCo5 Other workers4-' found the 1:2 compound in this series to exist in a C-15 (face-centered cubic) structure and the 1:5 compound to exist in a hexagonal crystal system. Comparison of earlier data with that now reported will be made subsequently. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been previously reported.' The cobalt content of alloy specimens was determined volumetrically. RESULTS Microstructure—The alloy containing 10.5 wt pct Co corresponds closely to the composition of the first intermetallic compound Gd3CO. In Fig. 1 the microstructure is essentially single phase composed of Gd3Co which formed peritectically. The globular areas are remnants of the peritectic reaction which did not quite go to completion. A eutectic occurs between Gd3Co and the next higher compound GdCO, which is followed by a series of peritectic compounds. Fig. 2, an arc-cast alloy containing 20.2 wt pct Co, shows large primary crystals of GdCo etching either white or black (depending on crystallographic orientation), embedded in the eutectic. Similarly, in Fig. 3 at 31.2 wt pct Co, a compound, probably GdCo3, has separated from the melt. Subsequent peritectic reactions were almost completely by-passed as the alloy cooled, the residual liquid freezing as a fine eutectic. In the 47.5 wt pct Co alloy, Fig. 4, the high melting point compound, GdCO4, has solidified as massive, white-etching grains, which reacted with the liquid to form GdCo3 as the second phase. The microstructure of an arc-melted alloy containing 60.5 pct Co is complex, Fig. 5, and presents some difficulty in interpretation. The grey etching matrix is probably primary GdCO4. The dappled phase represents grains of GdCO5 which have separated from the melt on cooling. The discrete spots in this phase are eutectic liquid. Small light etching crystallites are probably GdCO5 formed by the incomplete high-temperature peritectic reaction. GdCO4 is retained in arc-melted specimens containing 70.5 wt pct Co, Fig. 6. White areas of this compound are held in a matrix of GdCO5 the appearance of which is mottled slightly by inclusions of the second eutectic in this system. The development of the spheroidized eutectic at high cobalt contents is depicted in Fig. 7 (80.3 wt pct Co) in which the white massive crystals are GdCO5 compound. Further development of this eutectic is seen in Fig. 8, the primary white phase here being pure cobalt. Thermal Studies—Differential thermal analyses and melting point determinations have yielded the data shown in Fig. 10. The high gadolinium eutectic, indicated by microscopy, was confirmed at about 16 wt pct Co, melting at 620°C . A eutectic also occurs at about 84 wt pct Co melting at about 1260°C. The thermal arrests at 8803 960°, 1060; and 1210°C,

Jan 1, 1962

By Joseph Zwierzycki

By an extension of drilling activities in 1938, the Polish oil industry succeeded not only in maintaining production but even in increasing it slightly. This increase, however, was from present oil reserves and not due to the discovery of any new fields. Most of the new wells were drilled in the Jaslo district, particularly in the Lipinki-Libuszal oil field, because of the shallow depth of the producing sands. At the Boryslaw field the 12,332 meters drilled could not compensate for the steady drop in production. A drilling campaign similar to that of the previous year in the Stanislawow district resulted in a slight decline of production. A number of the new wells have been subsidized by the Fund for the Advancement of Drilling2 in Poland. As the present sums at the disposal of this fund are insufficient for a great exploration program, they are chiefly used for the maintenance of the actual production. New wells on known folds, but more than 1000 m. outside the present productive areas, are entitled to a subsidy. Applications for wildcats outside the known productive areas have not been received in 1938. Even when the Polish oil industry was prosperous, wildcatting was not frequent and in their present impoverished condition the oil companies are no longer able to bear such financial burdens. The only way to start a large-scale drilling campaign on the still existing promising areas seems to depend on the granting of new substantial subsidies from the Treasury. Such measures are being considered by the Polish Government. It has been suggested that a fund for wildcatting might be raised by a small increase in the price of benzine. An advance of one grosz per liter of benzine would raise, on present home consumption of 108,000 kilogram-tons, about 1.3 million zloty, an advance of 5 grosze more than 6 million zloty.3 This small increase in price would hardly be felt by the motor-car owners, as it would mean an extra expense of 80 to 400 zloty in a year.

Jan 1, 1939

By Joseph Zwierzycki

By an extension of drilling activities in 1938, the Polish oil industry succeeded not only in maintaining production but even in increasing it slightly. This increase, however, was from present oil reserves and not due to the discovery of any new fields. Most of the new wells were drilled in the Jaslo district, particularly in the Lipinki-Libuszal oil field, because of the shallow depth of the producing sands. At the Boryslaw field the 12,332 meters drilled could not compensate for the steady drop in production. A drilling campaign similar to that of the previous year in the Stanislawow district resulted in a slight decline of production. A number of the new wells have been subsidized by the Fund for the Advancement of Drilling2 in Poland. As the present sums at the disposal of this fund are insufficient for a great exploration program, they are chiefly used for the maintenance of the actual production. New wells on known folds, but more than 1000 m. outside the present productive areas, are entitled to a subsidy. Applications for wildcats outside the known productive areas have not been received in 1938. Even when the Polish oil industry was prosperous, wildcatting was not frequent and in their present impoverished condition the oil companies are no longer able to bear such financial burdens. The only way to start a large-scale drilling campaign on the still existing promising areas seems to depend on the granting of new substantial subsidies from the Treasury. Such measures are being considered by the Polish Government. It has been suggested that a fund for wildcatting might be raised by a small increase in the price of benzine. An advance of one grosz per liter of benzine would raise, on present home consumption of 108,000 kilogram-tons, about 1.3 million zloty, an advance of 5 grosze more than 6 million zloty.3 This small increase in price would hardly be felt by the motor-car owners, as it would mean an extra expense of 80 to 400 zloty in a year.

Jan 1, 1939

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.' Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.' The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By W. A. Backofen, D. H. Avery, G. A. Miller

An evaluation has been made of the relative importance of yield strength (?) and stacking-fault energy (y) to the rate of fatigue-crack growth in materials of fcc structure. Pure copper and its solid-solution al-loys with aluminum and nickel were chosen for the study because they provided sufficient range in both quantities of interest that either could be varied independently of the other. Experiments involved alternating tension and compression of flat specimens which were prepared with sharpened internal notches so that most, if not all, of the crack-nucleation interval could be eliminated. Growth rate (dC/dN) was concluded to be proportional to the square of the plastic-strain amplitude (€,,) over a strain range of approximately 6x 10-4 to 6 x 10-3. The factor, k, linking dC/dN and ep in dC/dN = kEp2 increased and decreased with corresponding variations in y, but it did not respond syste?>/atically to change in ay, indicating that y is the significant variable in crack growth at constant plastic-strain amplitude. In polycrystalline material, k varied by a factor of 5 over the available range of y. In a few single-crystal experiments on Cu-A1 alloys the growth rate responded less strongly to change in y. It has been suggested that single crystals behave somewhat differently than poly crystalline material because there is more extetnsive substructure near the grain boundaries in the latter, and this facilitates crack advance by separation along subgrain boundaries. A point of some controversy in current work on fatigue relates to the effects of strength and stacking-fault energy on crack growth. In recent experiments a separation was made between the cycling intervals for crack nucleation and the subsequent growth that eventually ends a specimen's fatigue life.' The study was carried out on Cu-A1 alloys primarily, fatigued in alternating four-point bending to constant deflection. A nucleation interval of about 10' cycles (at a total strain amplitude = 0.2 pct) was found to be insensitive to aluminum content in the range 0 to 7.5 wt pct, while the growth period was increased approximately forty fold over the same compositional range. The increase was not in any sense linear, however. Rather, most of the change occurred below 4 pct A1 or a stacking-fault energy, ?, of about 15 ergs per sq cm. It was argued that the plastic-strain amplitude was approximately constant, and therefore the effect of composition must have grown out of the reduction in stacking-fault energy. Several studies have shown that, with high ?, cross slip is encouraged, subgrain structure is introduced during fatigue, and cracking is aided through propagation along subgrain boundaries.1-5 Therefore, lowering ? sufficiently to interfere with substructure formation would be expected to retard growth rate. On the other hand, it is a general rule that resistance to fatigue cracking increases as strength is raised. Accordingly, there might still have been some doubt that Y was the controlling variable, since strength would be increased as y was lowered by the aluminum additions. To help in dispelling that doubt, an experiment was made on a polycrystalline Cu-Ni alloy similar in strength to the Cu-A1 alloys but of higher ?; the crack-growth interval was found to be essentially that of pure copper.' Further support for this position on stacking-fault energy as it relates to crack growth is derived from work by Boettner and McEvily,6 in which the actual crack-growth rate was measured on samples previously notched so as to minimize the nucleation period. Unfortunately, it was necessary in isolating strength level to compare different alloy systems and grain sizes. Recognizing the complication, it was still concluded that growth may be retarded by a reduction in y, per se. A related study has also been made by Roberson and Grosskreutz.7 The zinc content of a brass was systematically changed to alter strength and stack-ing-fault energy, although not below the 15 ergs per sq cm at which pronounced change in growth interval was found in the earlier work. The results were limited to more or less conventional S-N diagrams so that nucleation and growth events could not be separated. No definite conclusions were drawn, but

Jan 1, 1967

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.' This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6' At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963

By R. K. McGeary, B. Lustman

The textures produced in zirconium by cold and hot rolling, and by recrystallization above and below the transformation temperature were determined. Thermal expansivities were measured in the thickness, transverse, and rolling directions of preferentially oriented zirconium and were correlated with the texture scatter in these directions. REVIOUS investigations have indicated that minor differences between hexagonal close-packed metals of similar axial ratio may appear with respect to the textures produced both on cold rolling and on subsequent recrystallization. In the case of magnesium, beryllium, and titanium, metals of axial ratio similar to that of zirconium, the ideal orientations produced by rolling are fundamentally the same, although marked variance is reported in the degree and type of scatter about the mean orientation; in those instances where recrystallization textures were observed, they were reported to be similar to the rolling textures. Measurement of the anisot-ropy of thermal expansion of both rolled and re-crystallized zirconium could not be correlated satisfactorily with the textures reported for the above metals, and therefore a study was made of the preferred orientations produced in zirconium. Reported below are the textures produced in zirconium by cold and hot rolling, and recrystallization above and below the transformation temperature, together with the results of thermal expansion measurements. Determination of Preferred Orientation Two types of zirconium were investigated: 1— "crystal bar" zirconium obtained from the Foote Mineral Co., produced by the thermal decomposition of zirconium tetraiodide, and 2—zirconium ingot obtained from the Bureau of Mines prepared by melting sponge zirconium in a graphite resistor vacuum furnace in a graphite crucible. The major impurities present in the two materials used are listed in Table I. Several of the pole figures were later checked with 0.03 pct hafnium crystal bar material and the results were identical with those to be shown for the 1.5 pct hafnium material. The materials were cold rolled to 0.014 in. in thickness as shown in Table 11. Specimens were cut from the 0.014 in. thick rolled sheets and etched to thicknesses of 0.002 to 0.010 in. Such specimens were used for exposures up to a 50' to 60" angle between the beam and plane of the specimen; for higher angles a wire shape, similar to that described by Bakarian,' was formed on an end of the original 0.014 in. sheet. A fine-bladed abrasive cut-off wheel was used to slot the sheet and to form the cylindrical cross-section. The wire shaped ends were then etched to 0.006 to 0.010 in. in diam. Although absorption of X-rays in the wire-shaped specimens does not vary with angle of rotation, the line width around the diffraction rings was not uniform, because the wire was narrower than the X-ray beam, and this condition caused some uncertainty in the estimation of azimuthal intensities. Furthermore, scanning was not practicable with this type of specimen so that spottiness of the rings due to large grain size was excessive for specimens which had been heated above about 650°C. Nevertheless, satisfactory information could be obtained for high angle exposures from the negatives by the use of both types of specimens. Transmission Laue photograms were taken using unfiltered molybdenum radiation (47.5 kv, 18 ma) and a 0.025 in. pinhole. With the film 8 cm from a 0.005 in. thick specimen exposures of about 30 min were adequate. For specimens with a coarse grain size, a device that scanned about 0.15 sq in. of sheet surface was used. An attempt was made to plot the pole figures by use of an X-ray spectrometer as described by Norton.' However, for the particular technique used, the intensity variations obtained were not considered definite enough to give reliable results, especially for the large grained recrystallized and transformed specimens. This method was therefore abandoned in favor of the standard photographic method. Nine exposures were taken of each specimen: seven exposures with the beam perpendicular to the rolling direction and at 0°, 10°, 20°, 35", 50°, 65", and 80" to the transverse direction, and two exposures with the beam perpendicular to the transverse direction and at 60" and 80" to the rolling direction. Additional exposures were then made where necessary. The intensity variations of the diffraction rings were estimated by eye. It was usually possible to estimate 3 degrees of intensity from the photograms but in some cases 2, 4, or 5 degrees were estimated. Experimental Results The preferred orientation was determined for the following treatments: 1—cold-rolled, 2—low temperature rolled, 3—cold-rolled surface layer, 4— cross-rolled, 5—hot-rolled, 6—recrystallized below the transformation temperature, and 7-—recrystallized above the transformation temperature. I—Cold-Rolled Textures: The slip plane in hexag-

Jan 1, 1952