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By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By Patricia J. Rand, Kailish Narayan

Atlantic Richfield Co. began operating a commercial uranium solution mining project in April 1975, in Live Oak County, Tex., 10 miles southwest of the town of George West. The operation is designed to produce 250,00 lb of U308 per year and is jointly owned by Atlantic Richfield Co., Dalco, and U.S. Steel. The proprietary process employed in this operation consists of injecting an alkaline leaching solution into the ore-bearing formation through a pattern of injection wells. The uranium-bearing solution is then removed through producing wells using submersible pumps in central production wells. The produced solution is pumped through a pipeline to the plant area where the uranium is extracted. The barren solution is refurbished and returned to the pattern area for reinjection. The injection field and plant site are located in the drainage of Spring Creek, a small intermittent stream tributary to the Nueces River. Land use in the area is primarily agricultural cattle ranching and farming---but several producing gas fields are present in the areas as well. A nine month enviromental baseline study was conducted on the property beginning in Feb. 1975. Plants and animals of the Clay West area were identified and representative terrestrial and aquatic communities were analyzed. Physical and chemical parameters of the soils were described and analyzed. The surface and underground waters were analyzed chemically; radionuclides, heavy metals, nutrients, and pesticide concentrations were measured in the creek sediments; bacteriological measurements were made in creek water and sediments; radionuclide and chemical levels in plants and animals, both terrestial and aquatic, were measured. These studies, though not required by existing, state or federal laws, were considered necessary to assess the existing conditions before operations began on site. The in-place leaching technique for uranium mining eliminates the enviromental disturbances associated with open pit or underground mining. No grinding and crushing of ore is needed, nor are large tonnages of waste tailings produced. Surface subsidence is not expected since less than 5 lb of uranium is present per ton of rock and even complete removal of such small amounts should not cause subsidence. Solution mining has fewer environmental problems than conventional mining. Members of the Texas Water Quality Board recognized the differences which exist and have recently formulated new environmental control procedures which apply specifically to solution mining. Some of the solution mining activities which are of particular concern are discussed in the following pages. Process Description The produced uranium-bearing solution is pumped through a pipeline from the pattern area to the plant area. The first pattern area consists of a nest of 125 fluid injection, production, and monitor wells [(Fig. 1)]. Injection wells have 4-in. casings and are spaced 50 ft apart on a square grid. Production wells have a 6-in. casing and are located in the center of each square. A block flow sheet of the plant is given in [Fig. 2]. The produced solution goes through parallel trains, each consisting of a carbon column and an ion exchange column in series. The carbon column removes any sand present in the produced solution and the ion exchange column extracts the uranium. The depleted solution is treated with chemicals and returned to the field for reinjection. The uranium retained in the ion exchange column is removed periodically with a sodium chloride solution. Uranium-bearing solution from the ion exchange column is passed through a charcoal column for removal of impurities and then to a precipitation tank where the uranium is precipitated as yellowcake slurry. The yellowcake slurry is clarified, filtered and dried to produce a granular yellowcake product. Environmental Considerations Sources of waste solutions to storage reservoirs, the backwash reservoir and atmospheric discharges are shown in the block flow sheet [(Fig. 2)]. These waste solutions pose a relatively small problem and are adequately controlled by conventional means. There is one area, however,

Jan 1, 1978

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By T. L. Joseph

S. T. Killian (Johnstown, Pa.)—This is one of the finest papers I have read. Tying in stoichiometric calculations with furnace performance and practice is a step which had to be taken sooner or later. The noteworthy difference between Dr. Joseph's type of calculations and regular blast furnace calculations is that the Ib mol system is used as a basis. With the Ib mol system, weights, volumes, and chemical reactions can all be expressed in the same equation. In the paper, wind, ore, flux, and fuel are all expressed as lb or lb mols. Probably Dr. Joseph does not realize it, but the vague word coke appears only twice in the entire paper. Lb of C and Ib mols of C are followed through reactions but the word coke appears only as 1560 lb coke per ton of pig and 1700 lb of coke per ton of iron. Obviously in order to understand furnace reactions, the coke should be expressed as lb or lb mols of C. Furnaces can also be compared more easily. In some respects the paper is too thorough and too complete. The effects of the metalloids reduced into the iron upon the top gases represents a difference of less than 3 pct of the CO formed in the bosh. Due to the completeness of the calculations in relation to the CO/CO2 ratio, this was included and was necessary. However, the exclusion might have enabled more furnace men to follow the lb mol system of calculations through the blast furnace to a better degree. By considering only irons of similar analysis, this part of the calculations might have been omitted. However, if this had been done, total rewriting of the paper later would have been necessary in order to make the work complete as it is now. It also would not have been nearly as authoritative. In the paper, there appears the reaction: H2O + CO ? CO2 + H2 [I] Dr. Joseph states that he did not take this reaction into consideration in any calculations pertaining directly to the paper. The piobable reason- for this is that although it contains all the main reacting top gases except N2, it is rather inflexible since it is monomolecular in relation to each of the reacting gases and does not tie in with the gasification of C. Actually the reactions: H2O + C ? CO + H2 [2] 2H2O + C ? CO2 + H2 [31 and the solution loss reaction: CO2 + c ? 2c0 [41 tend to assume an equilibrium through the reaction: H2O + CO ? CO2 + H2 [I] which should be considered a balancing or equilibrium reaction. Reactions 2, 3 and 4 permit furnace conditions to balance with the CO/CO2 ratio and H2 formation. They tie in with the solution loss. Reaction 1 unites them chemically. Probably the best calculation to make at this time would be to try to find the relative importance of the CO2 from the flux and the H2 in the dilution on an actual furnace gas analysis. For this purpose the Dob-scha-Carnegie-Illinois paper—"Effect of Sized and Sintered Mesabi Iron Ores On Blast Furnace Performance" is chosen. This paper was presented before the blast furnace section of the AIME in 1948. This represents the best large scale furnace operation available to me. Unfortunately the changes were brought about by beneficiation of the burden and not by changes on one burden. In choosing the basis for the calculation in relation to the furnace, 100 mols of dry top sgas is chosen. This leaves something to be desired inasmuch as the nitrogen basis is changing but I believe it will be better understood than any other type and it is the easiest to use.

Jan 1, 1952

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 W. M. Myers

Certain minerals possess inherent color and other properties that make them suitable for the pigmentation of paints, mortar, plaster, concrete, face brick, and other materials. Their production is one of the most ancient of mineral industries and their use by primitive man is well known. These natural pigments have some economic factors in their favor, particularly wide geographic distribution, low cost of production, ease of preparation, chemical stability, and permanence in use so that they continue to form the basis of a small but useful industry. When used in paints such pigments act as a filler and supply body and opacity in addition to color. Natural mineral pigments are prepared for the market by the comparatively simple operations of washing, grinding, blending, and calcining. Any one, or all of these processes may be applied to a single pigment. The development of synthetic pigments and the use of byproduct materials have introduced competition with the products of nature and are having a growing influence on the economic position of the mined minerals. Development of the Industry The industry developed to commercial stature in Pennsylvania largely because of the presence of beds of ocher extending from Easton in a southwesterly direction toward Reading, and a variety of small iron mines in the region. The mining of paint ores in the Lehigh Valley was active as early as 1850 and shortly after the Civil War the establishment of mills expanded production and led to the development of new products and eventually the manufacture of synthetic pigments. Pennsylvania continues to maintain it.s leadership as a producer of mineral colors. Production is recorded also in New Jersey, Illinois, Virginia, Ohio, and Georgia. Iron as a Pigment Iron in various compounds is the most important pigment in nature. The iron pigments are characterized by stability, light fastness, good covering power, high index of refraction, and economy in production. Ferrous compounds display a typical green coloration. This has not been employed as a commercial pigment to any great extent except incidentally in such greenstones as have been used in construction, or crushed and sized for application as a granule to roofing. Ferric oxides are characteristically red and form an important group of industrial pignents. Hydrated ferric oxides exhibit various shades of yellow and are present in such familiar pigments as ocher and sienna. The addition of small amounts of manganese oxide or carbon as organic matter to the yellows produces the brown umbers. Magnetite is one of the few black minerals that grinds to a black powder. The mineral pigments vary from earth colors of low intensity and great dilution of iron content to almost pure iron compounds with high tinting strength and correspondingly greater value. There has been some relationship between the mining of iron ores and the production of mineral pigments; although the production of colors is not carried on appreciably as a byproduct of iron mining. A number of mineral pigment producers, particularly in the eastern states, have operated mines which in the past were small producers of hematite, bog ore, or carbonate ore. The knowledge of the location of the deposit and its possibilities as a producer of pigment are due to its past history as a producer of metallic ore. Many iron compounds may be changed in color by calcination, the end product being Fe2O3, a stable red oxide. The yellow hydrated oxides may be changed to red. The gray carbonate, found in Carbon County, Pa., calcines to a fine red product. Ferrous sulphate (copperas) often available in tonnage as a byproduct of the steel industry, breaks down under heat or chemical action leaving a residual red oxide. Pigments produced by calcination or dissassociation of compounds possess the advantage of fine particle size and ease of grinding. Mineral Pigments MINERAL BLACKS Many black minerals grind to a light colored powder. This characteristic is familiar to the mineralogist as the white streak produced by a black

Jan 1, 1950

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".' * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.' Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By U. Andres

U. Andres (The Technion, Haifa, Israel)-The authors are to be congratulated on their research, new and interesting, in a field which, however, the present writer and his assistants have been trying since 1962 to bring to the attention of the scientific and technical world, by means of publications covering several different aspects of this many-sided problem. We announced, in these publications, the results of magneto-hydrostatic (MHD) separation of magnetic and nonmagnetic minerals which we made in magnetic fluids (in paramagnetic solutions and suspensions of magnetic particles) which interact with permanent" and impermanent" inhomogeneous magnetic fields. There is no doubt that the authors have succeeded in creating ferrimagnetic colloids made by dispergation of 10-30 wt % of magnetite in kerosene in the presence of 7-10 vl % oleic acid. It may be judged by [Figs. 3 and 4] that the suspensions represent great stability systems and also "hysteresisless" fluids [(Fig. 5)] which bear witness to the existence of superparamagnetic suspensions. If the viscosity of these colloids is not so high, and the cost of preparing them can be covered, the fluids which have here been received can possibly be of interest to the technology of mineral separation. The potential possibility and technological perspective of similar media is demonstrated in our joint work with G. Bunin18 in 1965. The research carried out on the pushing out of cylinders and spheres from magnetic fluid is impressive; it would, however, have been interesting if the authors had compared their results with those on the pushing out of bodies from magnetic fluids adduced from our work." In my books" there happens to be described an experiment on the pushing out of a sphere in magnetic wedge field, in which the pushing out force of suspension with 5 vl % of magnetite reached 125 g per cc. This testifies to interesting possibilities of these media. Our works' shows also, on the basis of Laplace's equation the receiving of an interesting distribution of pushing out forces by selection of corresponding configurations of magnetic poles. Objection must be made to the authors' introduction of the term "antigravity force." The direction of this force does not depend on the direction of the gravity force and their opposition, i.e., antigravity is only one particular case. I am in full agreement with the authors' statement that magnetic pushing out forces "can be utilized to separate nonmagnetic objects according to variations in their densities." It is, however, necessary to make only one important addition, which can be found in our research on MHS at the Technion in Haifa, namely, that magnetic fluids in magnetic fields can be utilized in the separation of minerals according to variations in their magnetic susceptibility. The authors' conclusion is especially important considering the fact that in our publications" (including one in English") some designs of MHS separators and some technological results received on MHS-separators have already been described. S. E. Khalafalla and G. W. Reimers (Authors' Reply)We were aware (mostly through Chemical Abstracts of the American Chemical Society) of the use of solutions of paramagnetic salts such as manganous sulfate in agnetohydrodynamic separations by the Russian school headed by G. Bunin."n Professor Andres' contributions to this school are also evident in his application of the ponderomotive forces in an electrolyte placed in electric and magnetic cross-fields to separate coal and other useful minerals." It must be realized, however, that the foregoing research by Bunin et al." involved the use of magnetic fields and field gradients of very large magnitudes, i.e., such that H • grad H - 101 Oe2 per cm. The magnetization of paramagnetic salt solutions range from 0.1 to 0.5 gauss (at fields of a few thousand Oersteds) and never reach saturation. The magnetization of our superparamagnetic ferrofluids ranges from 100 to 500 gauss and reach saturation at fields of a few hundred Oersteds. Hence, to effect the same separation, the quantity "H

Jan 1, 1974

By J. R. Low, D. F. Stein

Single crystals of iron have been grown from three different lots of Ferrovac "E" of somewhat different chemical composition by the strain anneal technique. Using a technique to seed the crystal similar to Dunn's for silicon-iron, it has been possible to orient the crystals grown in both direction and plane of growth. Crystals having the plane of the strip oriented (100) , (110), (111), (112), (123), and (491) have been grown. The growth directions used have been [100], [110], 45 deg from a [110}, and various others of no specific crystal orientation. The usual dimensions of the crystals were 8 by 1 by 0.08 in. Attempts to grow crystals were about 90 pct successful. METHODS of growing single crystals of high purity iron have been reported in the literature.1-4 However, each of these methods was not completely reliable when used on materials having slightly different chemical composition and in some instances a small number of successes were obtained using identical materials. Except for the method used by S. Dohi and T. Yamoshita,1 it has not been possible to reorient single crystals of high purity iron to give any desired orientation. The method to be described has made it possible to grow single crystals from three different lots of material having different compositions, and to orient the crystals with respect to growth direction and surface. STARTING MATERIAL The material used during this investigation was a vacuum melted high purity iron marketed by the Vacuum Metals Corporation designated Ferrovac "E." Three lots of Ferrovac "E" having the following composition were used with equal success: The compositions listed are those of the as-received material; and they may have been modified before the growth of single crystals. Analysis of heat B just before growth and after growth revealed that the heat treatment prior to growth did not change the carbon content, but the oxygen content was changed from 0.0092 pct to 0.0034 pct and the nitrogen content from 0.0003 pct to 0.0001 pct. After growth of the single crystals, the carbon had dropped to 0.001 pct. None of the heat treatments would be expected to change any of the other impurities very markedly. Heat C would be expected to have a metallic impurity content similar to heats A and B. PROCEDURE Ferrovac "E" iron which had been obtained in bar form having a diameter of about 1 in. was rolled into strip for growing single crystals. By passing the 1-in. bar through a cold rolling mill several times, it was reduced to a strip 0.15 in. thick. The strips obtained were then cut into suitable lengths for heat treating (about 9 in. long), annealed at 925°C for 2 hr in dry hydrogen and water quenched. It was then necessary to bake the strip at 200°C for 24 hr in air in order to prevent cracking during further rolling operations. While it was possible to cold roll the 1-in. bar directly to the desired 0.080-in. strip, the intermediate anneal was used because the strip so obtained produced better single crystals. The strip obtained by rolling the 1 -in. bar directly to 0.080-in. strip produced single crystals having a large number of occluded grains. Experiments showed that the optimum reduction in area by rolling prior to the growth of single crystals was about 50 pct. Attempts to grow single crystals from material that had been reduced less than 40 pct were unsuccessful presumably because the matrix did not possess the critical amount of texture necessary for growth. The strip obtained after the rolling operations had very irregular edges which were ground to give a strip with uniform dimensions. The strip was then annealed at 825°C for 3 hr in hydrogen and furnace cooled. Fig. 1 illustrates the grain size obtained. A temperature of 940°C was used for the annealing temperature on one group of strips

Jan 1, 1962

By R. G. Knickerbocker, W. E. Brown, G. J. Vahrenkamp, M. M. Fine

THE results of a research and development laboratory and pilot-plant mineral-dressing investigation by the Bureau of Mines of the complex copper-lead-cobalt-nickel ores of southeast Missouri are reported in this paper. This investigation, in cooperation with the National Lead Co., showed that separate concentrates of lead, copper, and cobalt-nickel could be made by fine grinding and flotation. An industrial plant built subsequently by the St. Louis Smelting and Refining Div. near Fredericktown, Madison County, Mo., produced such concentrates during the war years. Present commercial production at the mill is limited to lead and copper concentrates, but research to permit economic utilization of the cobalt and nickel values is continuing. The complex sulphide deposits near Frederick-town in Madison County, Mo., have an operating history that dates back to the years preceding the Civil War. Perhaps these operations can best be summarized in terms of output which are given by Tyler: "Previous to 1900, the Mine la Motte Co. shipped cobalt ore to Swansea and in 1903 produced 120,000 pounds of oxide in a Missouri plant. Another cobalt refinery erected in 1906 by the North America Lead Co. at Fredericktown, Mo., operated intermittently until 1910. In 1909 it produced 83,384 pounds of cobalt oxide, 328,403 pounds of nickel, 8,314 tons of nickel-cobalt concentrates, 600 tons of copper concentrates, and 1,353 tons of lead concentrates. This plant was purchased at a forced sale in 1915 by the Missouri Cobalt Co., which produced a certain amount of oxide in 1918 and in 1920 recovered 102,410 pounds of cobalt oxide and cobalt hydrate, valued at $262,810." According to Buehler,2 "The ore, which consists of a complex mixture of the sulphides of cobalt, nickel, copper, lead, and iron, occurs at the contact of the pre-Cambrian porphyry and the overlying Lamotte sandstone and Bonneterre dolomite." The source of most of the cobalt and nickel is siegenite, a member of the linnaetite series of minerals. Its composition is variable, and although the chemical formula may be given as (CoNi),S,, it usually contains both iron and copper. The siegenite is characterized in this instance by an intimate association with chalcopyrite, and to a lesser extent with iron sulphides. Galena, on the other hand, while dis- seminated throughout the ore, is not closely bound to other constituents. Gangue is composed essentially of dolomite and quartz. Petrographic examination showed that fair liberation of sulphides and gangue could be attained at — 100 mesh. Complete liberation of micronsize inclusions, particularly of sulphides in each other would not have been possible at —400 mesh. Beneficiation Studies Many samples of the southeast Missouri ore were tested, but most of the work was confined to five samples of churn drill cuttings weighing 15 tons. The samples were reportedly representative of five sections of the deposit and were tested individually and as a composite. Only the results of the tests on the composite, which contained 1.28 pct lead, 2.03 pct copper, 1.06 pct nickel, 0.87 pct cobalt, 3.57 pct iron, 15.4 pct lime, and 23.9 pct silica, are presented in this report. In view of the rather complex and intimate association in the mineralogical composition of the ore, flotation was the logical choice in the selection of a beneficiation process. Other mineral dressing unit operations were considered as an adjunct to flotation, but none were beneficial. Many tests were made on these samples to determine the flotation characteristics of the mineral siegenite. As a result of this work, it was noted the siegenite was intermediate in floatability between chalcopyrite and galena on one extreme and iron sulphides on the other. The difference in floatability between siegenite and the iron sulphides was not very great and, in general, the same reagents that depressed pyrite and marcasite would also, in slightly larger quantities, depress siegenite. This tendency for siegenite

Jan 1, 1952

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By Cleland N. Conwell

APPLICATION of seismic methods to the location of buried channels in placer mining is fairly common knowledge, yet some of the facets of seismic refraction surveys have remained obscure in their application to mining. This description by a member of the U. S. Bureau of Reclamation team investigating bedrock at the Oso Dam site, may offer a lead to wider application of the method for bedrock determinations in engineering of mine and mill plants, tailing disposal, and water supply. It may also offer assistance in planning geological exploration in areas covered by overburden. Pertinent, and perhaps more than passingly significant, is that the seismic survey of the Oso dam site started at noon and was completed the afternoon of the next day. Location Oso dam site is on the Navajo River, Archuleta, County, Colo., 30 miles southeast of Pagosa Springs, Colo., 10 miles northwest of Chama, N. M. Bedrock at the proposed dam site is Mesa Verde Formation, Cretaceous age sandstone. The nearest good sandstone exposure is about 5/8 of a mile upstream from the location of the seismic determinations. The material above bedrock is sand and gravel with sandy loam soil covering benches above the river. The site appeared favorable, after a geologic and topographic reconnaissance, but overburden thickness was unknown. Exploratory drilling was not contemplated in the near future so a short seismic investigation was selected as the most suitable method of determining depth to bedrock. Field Procedure Geophysically, a seismic depth investigation is simply the measurement of depth from ground surface to the top of a layer which transmits seismic waves at a higher velocity. In this case the high-velocity seismic layer tentatively correlates with the Mesa Verde sandstone. Field procedure required a seismic explorationline or "spread" with 12 geophones set at measured intervals. Explosive charges were buried at few feet in the ground and detonated at shotpoints near the ends of the spread, and at intermediate points. The time of travel of the seismic waves from the shotpoints through the ground to each of the geophones along the spread was measured and recorded photographically with equipment housed in a field truck. The seismograph on each spread provided a time-travel graph. From it were computed the speed of seismic waves in various layers below the surface and depth to each different seismic layer below the shotpoint. In the case of the Oso dam site it was possible, in addition, to determine the depths below certain geophones, because there were only two seismic layers involved. Interpretation In seismic exploration waves are refracted from the top of layers which often correspond to divisions between subsurface formations. When drill holes are available the geologic logs offer a means of correlating stratigraphic breaks with seismic layers, improving reliability of seismic interpretation in terms of depth to bedrock or other geologic terms. There were no drill holes available in the case of the work at the Oso dam site. Geologic conditions appeared favorable for seismic technique because of excellent contrast in seismic wave velocity between the overburden and the Mesa Verde formation. The upper layer had a velocity of approximately 2500 fps and was interpreted as overburden, the lower layer had a velocity of approximately 9000 fps and was assumed to be the sandstone. These velocities are of the order expected in these materials. The seismographs obtained at the Oso dam site were excellent. The energy from the shot came in strongly at each geophone, giving an easily read record. Time-travel graphs plotted from wave arrival times were uniform and made interpretation comparatively easy. In Spreads 1 and 2 near the river the lower velocity layer was 12 to 15 ft deep. For the spreads on higher ground, or the bench south of the river, it was from 15 to 29 ft deep.

Jan 1, 1952

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2'3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,' and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By H. Rumfelt

The author demonstrates an approach for analyzing overcasting requirements for a stripping project. This approach to the problem employs indicated trends in the relationship of the weight of the machine (only electropowered draglines are considered) to its ability to do stripping work. Strip mining in the domestic coal industry is contributing a greater proportion of overall production than at any time in the past. U.S. Bureau of Mines statistics show that the percentage of total production mined in 1958 by stripping methods increased to more than 30 pct, up from 22 pct in 1951. The tendency to favor strip and open pit mining exists in other mining activities, but such trends are not as clearly outlined as in the coal industry. Significantly, the depth of overburden in coal properties considered suitable for stripping is also increasing. A depth of 50 to 60 ft of overburden was once considered to be about the maximum amount that could be handled economically. Today, a depth of 80 to 100 ft is frequently taken into consideration for simple overcasting operations (i.e., excavating overburden and dumping it in the spoil position where it remains indefinitely). Accompanying these changes, there have been continuing studies searching for procedures to appraise deeper stripping problems. Although the only known practicable way to accurately evaluate a proposed stripping venture is to make studies (including cost estimates) step by step, it is nevertheless desirable to have a quick method for making preliminary evaluations of potential strip mining operations. A recently devised digital computer method of providing a preliminary simple overcasting analysis for a stripping prospect relates the indicated trends in the relationship of the weight of the machine to its ability to do stripping work. In addition, this approach employs situations where the geometry of each cut-and-spoil section is assumed to take certain defined relationships for varying overburden depths. Slopes are necessarily considered to be stable, which means such practical factors as the mechanics of soils are neglected for the sake of convenience. Definition of Terms: Photographs A and B show a shovel-type and a dragline-type of simple overcast operation, plus terms used to denote certain parts of a pit. Pits that follow a straight line when projected on a horizontal plane are referred to as straightaway. It has been assumed that all section drawings accompanying this article pertain to straightaway cuts which, in turn, means that areas can be compared by relative volume. The volume of overburden is measured in virgin cubic yards. Material displaced from its virgin state to a spoil area normally occupies a larger volume than when in situ; the difference is termed swell, and it is expressed as a percentage of the original volume. For example, if the original cut volume is denoted V cu yd, and the spoil volume is 1.2 V cu yd, the swell is a positive 20 pct. MAXIMUM USEFULNESS FACTOR (MUF) CONCEPT Men experienced in overburden removal give emphasis to the weight of the machine in relation to its value as an excavator. From the writer's understanding, value has been only loosely defined and discussed generally and vaguely. The concept is considered important, however, since it is based upon the observations of many men. It provides a clue for the approach taken to solve deep stripping problems. In the procedure described below, value has been arbitrarily established as the product of the nominal dipper size of the shovel (or dragline) times a functional dumping reach. MUFs—Shovel: A shovel's capability to handle thick overburden is usually limited by its ability to dispose of the spoil. Thus the dumping reach, as well as its dumping height, is significant. The angle of repose of spoil material must also be considered. Although such slope angles vary among different mines, jobs, and materials, a slope of 1.25 to 1, frequently found in both planning and practice, is used by this author in the illustration of this analytical method. The relationship of the shovel's geometry to a stripping operation is shown in Fig. 1. To gain maximum advantage in constructing spoil piles, the shovel is placed so that its tracks adjacent to the spoil are as close as possible to the rib of the coal deposit. A vertical plane passing through the line

Jan 1, 1961

By Robert U. King, John W. Vanderwilt

THE Climax molybdenite deposit in Lake County 100 miles southwest of Denver is located in the central part of the mineral belt extending northeasterly across the state. Principal geographic features and geology are shown on Fig. 1. The first period of molybdenite mining, which began in 1918, ended in April 1919 because of limited demand and a price drop to about 72¢ per lb. During this time the ore came from the Leal level and surface outcrops at a higher elevation. Rate of mining was 250 tpd and several million tons of ore averaging 0.7 pct molybdenite were developed. Since April 1924, when the second period* began, Climax Molybdenum Co. has been the only operating company. Production in 1924 was 400 tpd and finding ore was a continual problem. When the White tunnel was extended, however, further ore was encountered. The orebody was thought to be tabular until 1926, when B. S. Butler recognized the relation of the developed ore on the Leal and White levels to a central area of fine-grained hydrother-mal quartz, and by 1929 diamond drilling had blocked out indicated ore reserves in excess of 100 million tons. In 1946, on the basis of information obtained from 25 miles of mine workings and a completed exploratory program involving over 200,000 ft of diamond drilling, the present authors reviewed and brought up to date the geology of the orebody. More recently Sears," employing microscopic techniques, made a study of hydrothermal alteration and mineralization, and Howell and Schassberger'" restudied available geologic data. Production (1953) of molybdenite ore has been expanded to over 25,000 tpd and total production from 1918 through 1953 has been: Tungsten, tin, and pyrite are byproducts and monazite also was produced from 1949 through 1951, after which it was not saved. A maximum of 15 to 20 tons of monazite was produced. Geology of the Area Pre-Cambrian crystalline rocks constitute most of the Mosquito Range for several miles to the north, east, and south of the Climax molybdenite deposit, see Fig. 1. To the west the crystalline rocks are in fault contact with shales and sandstones of Pennsyl-vanian age. Both crystalline rocks and sediments are intruded by dikes and sills of Tertiary age. Numerous faults with small displacements are to be found in the crystalline rocks east of the Mosquito fault and in the sedimentary beds to the west. Pre-Cambrian Rocks: The pre-Cambrian rocks consist of schist and gneiss, identified with the Idaho Springs formation, and granite with minor pegmatite correlated with the Silver Plume granite of the Silver Plume area. The Idaho Springs formation is a general term applied to pre-Cambrian schist and gneiss found over a large part of the Colorado Front Range. At Climax this formation consists largely of biotite-schist and quartz-biotite gneiss with minor quantities of plagioclase and orthoclase, although in places appreciable quantities of feldspar and quartz are present in the more gneissic varieties. Locally, especially along the contact with granite, recrystal-lization of the schist has produced coarser texture and a more pronounced than average gneissic appearance. The gneiss and schist have been mapped as a single unit by Butler and Vanderwilt (1933)" and by Singewald (1951).12 Schist predominates at the higher elevations of the Mosquito Range and in the area to the north and east of Climax. The regional trend of schistosity is northeast with varying dips to the east. Silver Plume granite and associated pegmatite intrudes the Idaho Springs formation. Silver Plume granite in many places and in the Climax district in particular has an irregular form, and many large and small inclusions of schist and gneiss occur within the granite. Granite predominates at the surface in the immediate vicinity of the area of hydrothermal alteration and extends for several miles to the northeast and southeast. As more schist is present at lower levels of the mine than in the upper levels, the suggestion is that the granite is sill-like in form,

Jan 1, 1956

By J. W. Freeman, E. E. Reynolds, A. E. White

Fram a study of 63 systematic alloy modifications it was found that molybdenum, tungsten, and columbium, added individually or simultaneously, and increases in chromium cause major improvements in 1200°F rupture strengths of Cr-Ni-Co-Fe base alloys. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. THIS paper describes the results of an investigation of a series of alloys with systematic variations of the chemical composition of the following basic alloy: C, 0.15: Mn, 1.7; Si, 0.5; Cr, 20.0; NI, 20.0: Co, 20.0: Mo, 3.0; W, 2.0; Cb, 1.0; N, 0.12; Fe, 32.0 pct. The 62 modifications of this alloy were produced under conditions which minimized all factors influencing properties at high temperatures except composition. Melting, fabrication, and heat treatment were carefully maintained constant. Stress-rupture properties at 1200°F were used as the primary criteria of evaluation of the alloy. The objective of the study was to obtain data for determining the fundamental role of the influence of alloying elements on properties of heat-resistant alloys at high temperatures. In addition the results should be useful in determining optimum chemical compositions, the sensitivity of properties to variations in composition, and the degree to which alloy content could be reduced while retaining worthwhile properties. It is difficult or impossible to develop correlations between properties at high temperatures and systematic variations in chemical composition from published data for wrought heat-resistant alloys developed for gas turbines.' ' The main reason for this is the extreme dependence of the properties on conditions of treatment of the alloys." In most cases variation in final treatments between alloys so influences the properties that the influence of chemical composition is obscured. In addition it is recognized Table I. Basic Alloy and Some Modifications Used Basic AllOy, Variations in Element Pct Composition, Pct C 0.15 0.08. 0.40. 0.60 Mn 1.1 0.03,0.25.0.50,1.0,2.5 S1 0.50 1.2, 1.6 Cr 20.0 10, 30 Ni 20.0 0, 10,30 Co 20.0 0. 10, 30 MO 3.0 0. 1.2.3, 5, 7 W 2.0 0, 1, 5, 1 Cb 1.0 0.2,4,6 N 0.12 0.004, 0.08, 0.18 Fe 32.0 that variations exist between heats of the same alloy which are related to melting practice and that there is a strong possibility that conditions of hot working influence response to final treatments. The development of heat-resistant alloys has been based on the gradual accumulation of data roughly related to composition from extensive testing programs. There is every reason to believe that in most cases the optimum compositions have been achieved by this procedure in the alloys commercially available. There are, however, very little data showing the influence of systematic variations of composition free from the influence of other factors, particularly for alloys of the type investigated. Several investigators of cast alloys have demonstrated compositional effects, notably Grant,1-6 Epremian,t Guy,8 and Harder and Gow.9 Sykes10 eviewed the work on the wrought alloy Rex 78 and the systematic variations of carbon, copper, molybdenum, and cobalt leading to the development of the stronger Rex 337A alloy. From the papers by Wilson11 and Henry12 it is possible to deduce the beneficial effect of substituting cobalt for iron in 0.45 pct C-20 pct Cr-20 pct Ni-4 pct Mo-4 pct W- 4 pct Cb alloys. Wilson mentioned but did not present the extensive compositional studies involved in developing these alloys. Binder" showed optimum properties for 3, 2, and I pct, respectively, for molybdenum, tungsten, and columbium in 20 pct Cr-20 pct Ni-20 pct Co-30 pct Fe alloys for limited systematic variations of these

Jan 1, 1953

By W. F. Hower, W. Brown

Large-scale sand consolidation tests were conducted in an effort to determine the reasons for the successes and failures of this method of sand control. Several different consolidating materials were used in treating both clean and bentonitic sands that were packed in a chamber having a capacity of 3.3 cu ft. The results were essentially the same for all of the different consolidating materials, The data show that low-viscosity consolidating materials pumped at a relatively slow rate gave the best results. Where the formation has produced sand, the treating fluids can compress the formation, thus permitting the channeling of fluids to another horizon. Pressure-packing these zones before attempting to consolidate is recommended. Sands containing more than 4 per cent of water-swelling clays are not good candidates for consolidation. It is indicated that loose sand, particularly when it is bentonitic, can be fractured during the placement of the treating fluids. INTRODUCTION Sand production in oil and gas wells has plagued the industry for many years, and numerous cures for this problem have been suggested. Most methods have been successful to a certain degree, but the great variety of well conditions that exist in the different areas has magni- fied the problem and limited the successful use of the various systems. Four review papers1-4 present a wealth of information concerning the degrees of success that have been obtained by the different sand-control methods. The bridging of sand grains by the use of gravel packs and screens has been quite successful. However, these methods do not leave the casing clear for all types of multiple completions, and the cure does not last for the production life of the well in some instance:;. The control of loose sands by sand consolidation with resins has never been as successful as desired. It has always been hoped that such a treatment would eliminate all sand problems for the life of the well, but. initial applications, starting in the middle 1940's, were only moderately successful. Lott, et a1,3 reported a success ratio of approximately 50 per cent and made the following conclusions. The highest percentage of successes were obtained where: a. Consolidation of a zone was made at the time of initial completion or prior to the production of sand. b. The interval treated was less than 12 ft in length. c. Between 30 and 50 gill plastic/ft of producing interval was displaced through the perforations. REASONS FOR SAND CONSOLIDATION FAILURES Our own experiences in the field of sand consolidation point toward the following conditions as the major reasons for the failure of sand consolidation attempts. 1. Mud-plugged perforations and mud invasion of the formation. 2. Sand in the casing covering all or part of the perforations. This sand could be either formation sand or one of the coarser sands used as propping agents in hydraulic fracturing. 3. Holes in the casing. 4. Channels behind the casing. 5. Attempting to treat too long a perforated section. 6. Too high a percentage of water-swelling clays in the formation. 7. Formations that have produced sand. Recent attempts were made to treat perforated sections ranging from 10 to 30 ft, in wells that have produced sand, by using a straddle packer that was raised and lowered through the perforations as the consolidating material was being pumped. In most instances, the pressure required to pump fluid into the formation varied considerably as the tool was raised and lowered. This suggested the possibility that significant differences in permeability were present or that only part of the formation had produced sand. There were times when a sudden break in pressure indicated that a fracture was being formed. Research conducted several years ago concerning the problem of the control of water in air and gas drilling indicated that shale sections could be fractured quite easily. In addition, it was determined that it was easier to pump fluids into shale bodies by fracturing the shale itself, or the interface between the shale and sand, than to pump into a fluid-saturated formation. Formations that produce sand are usually adjacent to shale bodies and frequently have shale streaks of various thicknesses inter-bedded in the sand. Therefore, where shale is exposed to fluid pressure it

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970