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By B. H. Kear

All the possible ways of forming simple two-dislocation boundaries in multiple slip orientations are deduced. It is shown that the principal differences in work hardening behavior of crystals plastically deformed in these orientations can he accounted for in terms of the likelihood of formation of diffuse boundaries, or deformation bands, consisting of the products of dislocation reactions of the Lomer type. Also, it is pointed out that the break-up of boundaries under the applied stress is more likely to yield interstitial jogs than vacancy jogs, whereas glide dislocations cutting throuqh dislocations trapped in particularly stable boundam'es can acquire both types of jogs. USING Frank's' grain boundary formula, Ball and Hirsch2 determined the parameters of all the possible boundaries that can be built from two sets of glide dislocations in the fee structure. This paper deduces the geometrical possibilities for the formation of these two-dislocation boundaries in the different multiple slip orientations, and discusses the role of boundaries in work hardening and in jog formation. Formation of Two-Dislocation Boundaries in Mutiple Slip Orientations. The parameters of the possible two-dislocation boundaries for any crystal orientation can be deduced most conveniently using the boundary formulae due to Amelinckx,3 in conjunction with the stereographic projection shown in Fig. 1. Suppose that slip occurs in a-BC and ß-CA. According to Amelinckx, when the two systems of glide dislocations are parallel, the rotation axis, u, of the boundary is parallel to (a x ß) and the unit normal, u, defining the boundary plane is parallel to (a x ß) x (BC x CA). On the other hand, when the glide dislocations form a crossed grid, u is parallel to (BC x CA) and u is parallel to (a x CA) x (ß x BC). In Fig. 1, (a x ß) is the pole of the great circle passing through a and ß, so that u is parallel to DC, i.e., parallel to [110]. Furthermore, (a x ß) x (BC x CA) is the pole of the great circle passing through DC and 6, so that u is parallel to [110]. Hence, when all the glide dislocations are parallel, the boundary is pure tilt with parameters u = [110], v = [ 110]. Similarly, it may be shown that the corresponding crossed grid of dislocations is a mixed boundary with u = [111], u = [111]. Consider the case of a crystal compressed in the [001] orientation. In this orientation, according to Fig. 1, there are eight available slip systems. In what follows, the different types of two-dislocation boundaries that are possible in this orientation will be examined by taking different combinations of two slip systems out of the available eight, with a-BC always one of the systems. Case (i)—Slip Systems a-BC and d-CB. The formation of a tilt boundary in (101), which consists of a crossed grid of edge dislocations with vectors BC andCB, is illustrated in Fig. 2(a). As the figure shows, slip is required in the system a-BC in one part of the crystal and in d-CB in the other part, with both sets of dislocations entering the boundary from opposite sides. The rotation axis of the boundary lies in (101), depending on the relative densities of the two sets of edge dislocations in the boundary. Case (ii)-Slip Systems a-BC and ß-CA. The two possible boundaries are shown in Figs. 2(b) and (c); boundary (b) is tilt with u = [110], u = [110], and

Jan 1, 1962

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By C. J. Bechtoldt, H. C. Vacher

Quenched alloys, prepared by powder metallurgical techniques, were examined by microscopic and X-ray diffraction methods. The compositions and heat treatments were chosen so that the chromium and nickel solvuses could be determined and a range of composition and temperature, in which a eutectoid had been reported, could be explored in small intervals. The results showed no evidence of eutectoid reactions having taken place. ALLOYS containing iron, chromium, molybdenum, and nickel are extensively used in high-temperature applications. In order to provide basic information on the solid-state reactions that occur in such alloys, the National Bureau of Standards is engaged in an extensive study of the equilibrium phases in the binary, ternary, and quaternary systems involving these four metals. Attention was directed to the chromium-nickel system because a review of the literature showed conflicting data. A recent compendium1 of the constitution of binary alloys gives two diagrams for the chromium-nickel system, one a simple eutectic and the second a diagram showing a eutectoid and a eutectic. The eutectoid was the result of an allotropic transformation in a high-temperature solid-solution form of a chromium-rich phase called 0. The approximate temperature and composition of the eutectoid was 1200°C and 30 at. pct Ni. In the preliminary study, at the Bureau, no transformation was indicated in the chromium-rich phase of ternary and quaternary alloys in which chromium and nickel were major components. Similar results have been reported from time to time in the literature,2-8 In consequence of this situation, a systematic study was made of the constitution of heat-treated chromium-nickel alloys using metallographic and X-ray diffraction methods. The compositions of the alloys were selected so as to determine the boundaries of the chromium-rich and the nickel-rich phases and to explore in small intervals the ranges in composition and temperature in which the eutectoid had been reported. The results of this study are reported and discussed in the present paper. EXPERIMENTAL PROCEDURES Materials, Alloys, and Heat Treatments—The alloys were prepared by a powder metallurgy technique similar to that used in earlier work.9 Analyses of the materials used are given in Table I. Powders were mixed using a vibrator in 30-g batches of predetermined composition; 2-g pellets were made from the mixture by compacting at room temperature in a 1/2-in. diam mold under 60,000 lb per sq in. pressure. The pellets were sintered in dry hydrogen for 10 days at 1300°C. At the end of the sintering treatment the specimens were quenched in water, which caused a pale green film to form on the chromium-rich alloys and thin black scale to form on the nickel-rich alloys. The pellets after sintering were approximately 1/2 in. diam by 3/32 in. thick. The purification train9 was modified by inserting a tube of titanium turnings, heated at 700°C to increase the efficiency of the removal of oxgen and nitrogen. It was found in the earlier work that the sintering treatment lowered the carbon, oxygen, and nitrogen contents of chromium-rich alloys to 0.01, 0.01, and 0.004 wt pct, respectively, and that there was a loss of chromium. In order to ascertain the extent of this loss, the chromium contents of certain alloys were determined chemically. They included those alloys used to determine the parameter-composition curves and those of critical composition, used to determine the chromium-solvus microscopically; these analyses were made on samples after the final heat treatments. The mixed powder values for the chromium content of those alloys that were not analyzed were adjusted to conform to a smooth curve based on the chemically analyzed values for

Jan 1, 1962

By C. M. Schwartz, A. P. Young

ZIRCONIUM is noticeably embrittled at room temperature by hydride precipitate not only in notch-impact tests but also in tensile-impact tests.&apos; The embrittlement in slow-strain tensile samples is much less severe. To understand better the relationship of the hydride precipitate to the strain-rate effect in tensile samples, the surfaces of chemically polished zirconium tensile samples strained at a slow rate (0.03 in. per min head speed) and at an impact rate (18.1 fps hammer speed) were examined in the light and electron microscopes. Vacuum-degassed samples and hydrogenated samples (100 ppm hydrogen) were examined. The hydrogenated samples were slow cooled from 800°C. The most apparent difference between slow-strain and impact tensile samples was the preponderance of twinning over slip in impact samples as opposed to relatively little twinning in slow-strain samples. The twin bands in hydrogenated samples often terminated on hydride needles as seen in Fig. 1. Almost opposite the twin terminus is a fine crack and a nearly round fissure. Holes near the areas where single lens-shaped twins or opposing pairs terminate on hydride particles also could be seen In the light micrbscope. Quite frequently, microcracks associated with a partial row of hydride particles were visible, as in Fig. 2, indicating that the crack was parallel to a row of hydride particles. Some samples were chemically polished after straining to remove metal with a minimum of disturbance of internal voids. Fig. 3 shows a crack in the interior of a hydrogenated impact sample. Holes along grain boundaries were seen after impact in both degassed and hydrogenated samples. Very few microcracks were seen in degassed samples after impact or slow strain, or in hydrogenated samples after slow strain.

Jan 1, 1959

By G. Sherburne Rogers

One of the features of oil-field work that puzzles operator, chemist, and geologist alike, is variation in the gravity of the petroleum produced on neighboring leases or even from adjoining wells. Few fields in the United States yield oil that is of uniform gravity throughout; in some fields the different grades are produced from different sands, in a few from different formations, and in many from different areas in the same sand. In a few cases, perhaps, a common assumption—that the heavier oil is derived from the lighter through the escape of the more volatile constituents—is valid, but many cases can not be explained in this way. Although in the California fields the specific gravity of the oil generally decreases with depth, there are numerous exceptions to this rule; and, as in many other regions the light oil is found nearest the surface, it is evident that evaporation underground is generally an unimportant factor. It is generally recognized that the great differences between petroleum from widely separated fields are due largely to differences in age and degree of metamorphism and to variation in the composition of the original organic matter; but in the writer&apos;s opinion some of these broader differences, as well as most of the minor variations in the character of the oil from any one field, are due to the local action of natural reagents such as sulphur or oxygen. This is particularly likely to be true if the oil has migrated from one formation to another, as in the California fields; and in some arcas it appears that variation in sulphur content may even afford a rough index of the extent or distance of the migration. It is the purpose of this paper to call attention to the chemical action of sulphur and oxygen on petroleum, to show that the gravity of the oil from any one field is intimately related to its sulphur content, and to discuss the possi-

Jan 1, 1918

By G. St. J. Perrott

One of the important hazards in coal mining is the danger of ignition of explosive mixtures of methane and air or coal dust and air, or both, by the explosives used in blasting the coal. It has long been recognized that certain explosives are more dangerous than others in this respect. &apos; In America and abroad, government testing stations have been established for officially passing on the suitability of explosives for use in coal mines. In this country the Federal government is given no power to enforce the use of the approved explosives but merely publishes from time to time, through the Bureau of Mines, those explosives which have passed the tests necessary to place them on the list for use in coal mines. In spite of this lack of police power, the increase in the use of permissible .explosives since the promulgation of the fist list in 1909 has been rapid. In 1912, only 8 per cent. of the explosives used in coal mines were permissible; in 1925, this figure had increased to 25 per cent. While the past record of permissible explosives has been most gratifying, it is very desirable that we pave the way for further improvement in explosives and blasting methods by learning more about the mechanism of ignition of gas and coal dust by explosives. To this end a considerable amount of investigative work already has been carried out and a large amount yet remains to be done. It is the purpose of this paper to discuss briefly the effect of the characteristics of explosives and method of loading in the borehole on the liability of a blown-out shot to ignite explosive mixtures of gas or dust. For an account of the methods by which an explosive is tested for permissibility for use in coal mines, the reader is referred to Schedule 17-A of the U. S. Bureau of Mines. Safety Factor in Using Explosives The factors that affect the liability of an explosive to ignite gas or dust are already known in a qualitative way but quantitative data are

Jan 1, 1927

By T. T. Chen, P. Pint

Based on the mineralogy, phase characteristics and compositions of the smelter feed, the smelter products and the smelter wastes, the sources and distributions of mercury and arsenic in the Afton copper smelter, Kamloops, British Columbia have been determined. Of the total mercury In the feed, approximately 33% is in solid solution in tennantite, 51% is in native copper and 16% occurs as mercurian silver. Arsenic in the feed occurs mainly as tennantite. Under current smelting conditions, 99.6% of the total mercury In the feeds enters the off-gas cleaning system. From this off-gas, about 1% of the total mercury, occurring as dust, is recirculated to the flotation concentrate; 4.6% of the total mercury is contained in SO2 scrubber sludge which is discharged to tailings. Approximately 78% of the total arsenic in the smelter reports in the copper products; 20% is incorporated in the dust and slag which are subsequently recirculated to the mill. Only 1.8% is rejected as scrubber sludge, and less than 0.2% 1s released to the mercury scrubber.

Jan 1, 1984

By J. W. Rutter, K. T. Aust

THE object of the experiments to be described in this report was to determine, first, which grains, out of a large number introduced into a sample in which their growth could proceed, were able to grow most successfully; and, second, the factors which control their growth selection. In an earlier study of grain boundary migration in high-purity lead,&apos; it was found that, under some conditions, the most successful grain in an experiment of this type bears a special orientation relationship to the grain into which it is growing. The present work represents an extension of the previous study, directed at the determination of the orientation relationships which appear under a wider variety of conditions. Experiments of this general type have been done using commercial aluminum2 with somewhat conflicting results. In the present experiments, in contrast to the above,&apos; the sample composition was a principal controlled variable, resulting in a considerable clarification of the phenomena observed. EXPERIMENTAL TECHNIQUE The experimental technique used in this investigation was essentially that employed previously in studies of grain boundary migration kinetics.1&apos;3 The material used was zone-refined lead with various small amounts of tin or silver added to study the effect of varying the sample composition. The specimens were in the form of single crystals, about 1/4 in. 1/4 in cross section by 3 to 4 in. in length, grown from the melt in a horizontal graphite boat. A crystal grown in this way generally contained a lineage or "striation" substructure of the type shown in Fig. 1 of Ref. 1. This substructure consists of an array of low-angle boundaries which partition the crystal into regions misoriented from each other by a few degrees. The substructure constitutes a source of driving energy, estimated to be about 4000 ergs per cc, for the migration of a large-angle grain boundary into the striated crystal. New grains were introduced by plastic deformation in compression of a localized reglon at one end of the sample. Re-crystallization occurs at room temperature in the deformed region, introducing a large number of new, striation-free grains into the specimen. These grains are able to grow into the melt-grown crystal on annealing at a suitable temperature. The stria-tions are removed by passage of the grain boundary, as the substructure energy is utilized to produce the boundary migration. Usually, only one or two of the recrystallized grains persist after growth has occurred for about 1 cm out of the deformed region. Laue back-reflection X-ray photographs were obtained to determine the orientation relationship between the melt-grown crystal and the recrystallized grain or grains which grew most successfully in each specimen. EXPERIMENTAL OBSERVATIONS Fig. 1 shows the results obtained for a series of specimens to which had been added tin in the range from 0 to 5 ppm by weight. In this figure is plotted, in the standard stereographic triangle, the single axis about which the most successful recrystallized grain or grains are related to the starting, melt-grown crystal by the smallest rotation. The range of angular rotations observed about such axes is indicated beside each stereographic triangle. The results shown in the stereographic triangle on the left, Fig. l(a), were obtained by localized deformation at one end of each specimen at room temperature, followed by annealing in a furnace which had been preheated to 300°C. The furnace atmosphere was argon. It will be seen that the orientation relationships observed between the melt-grown and recrystallized grains are quite random. On the right, Fig. l(b), are shown results for samples in which the de-

Jan 1, 1961

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen&apos; determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By Joseph C. Kieffer

THE Duquesne property of the Callahan Zinc-Lead Co. is about 20 miles east of Nogales, in southern Arizona. One mine is near the mill, but most of the mill feed is hauled in by truck from a number of small mines. The same sulphides are found in all the ores, in general, but the amounts vary considerably. All ores contain silver, copper, lead and zinc minerals but one mine ships ore high in silver and lead and low in copper and zinc; while another mine ships ore high in copper and zinc, and low in silver and lead. The common sulphides are galena, carrying most of the silver; chalcopyrite; sphalerite, carrying iron in solid solution; and pyrite, in a gangue consisting of limestone, quartz and garnet. Mineralization is fairly coarse. At the present grind of about 66 per cent minus 200 mesh most of the sulphides are liberated. A small amount of chalcopyrite is locked up with the sphalerite and cannot be liberated at an economic grind, and the copper carried into the zinc concentrate with the sphalerite accounts for the comparatively poor recovery of copper in the copper-lead concentrate. PRODUCTION OF TWO CONCENTRATES The milling problem, which was complicated by the extreme variation in the grade of the feed, was first attacked with the idea of producing a silver-copper-lead concentrate and a zinc concentrate, both with satisfactory grades and recoveries. By February I94I, it was felt that these objectives had been attained, when the grades of the various products and the recoveries were as shown in Table I. [ ] A rough outline of the flowsheet and reagents used is as follows: Minus ¾ -in. feed to a 7-ft. by 36-in. Hardinge ball mill working in closed circuit with a 36-in. Wemco classifier. The classifier overflow passes to the second cell of an 8-cell bank of No. 18 Special Denver Sub-A flotation machines (volume, 22.5 cu. ft. per cell). A rougher concentrate is removed from the second to the fifth cells inclusive, and returned to the first cell, which is the cleaner. A scavenger concentrate is removed from the sixth, seventh, and eighth cells, and returned to the third cell. Consump

Jan 1, 1942

By Ronald W. Klusman, Erik B. Nelson

The Front Range portion of the Colorado Mineral Belt is an extensive area of mineralization with mining activity dating from 1859 with the discovery of large gold deposits. After an initial boom period and gradual diminishing production, present activity is restricted to molybdenum in Clear Creek County, uranium in Jefferson County, and several small operations extracting gold and silver in Clear Creek and Gilpin Counties. Gold and silver have dominated the production in the Front Range, though the complex mineralization created milling and smelting problems and it is postulated that considerable amounts of precious metals remain in the mine dumps. This area is plagued by a severe mine drainage problem, with Clear Creek most impacted by many draining mines and tailings in the basin. Boyles et al. Moran and Wentz, Wentz, Wildeman et al., have examined various aspects of the impact of mine drain¬age in the Clear Creek basin. The primary objective of this study was to collect data on the tailings, drainages, and leaching experiments in order to make preliminary suggestions for reducing the impact while recovering metal values to offset treatment costs. A variety of leaching experiments were performed on tailings from the Nevada Gulch area in the Central City mining district. Leachings were performed in vertical tubes indoors and wooden boxes exposed to the outside environment. In the leaching experiments, the leaching solution, grain size, and residence times were varied, while forced aeration was used in some experiments. Bacterial nutrient 9K° and mine drainage were used in some of the experiments. A total of 14 additional tailings samples were analyzed for base and precious metals. The composition of the mine drainage and tailings used in the leaching experiments, as well as data on the additional samples are shown in [Table 1]. Leachate samples were taken periodically for analysis until compositions leveled off. Results and Discussion Leaching with distilled water was used as a control and best illustrates the basic behavior of the leaching process for zinc in a vertical tube [(Fig. 1)]. More acidic leachings increased concentrations of metals as did smaller grain sizes, though the time required increased significantly. Mine drainage with its high concentration of dissolved iron sometimes decreased the heavy-metal concentration in the leachate due to oxidation of Fe 2 and precipitation of Fe(OH)9 which absorbs some of the dissolved heavy metals. In the larger scale experiment carried out in the simulated leaching pad, substantial concentrations of metals were attained in the final leachate after one month. In this experiment the leachate was not recycled, but allowed to saturate the tailings continually with evaporation loss made up by additions of Quartz Hill drainage and nutrient 9K. The concentration of the metals in the leachate and the increase over the input solution are given in [Table 2]. Heap leaching of low-grade copper and uranium ores is successfully carried out in many districts, enhanced by the metabolism of autotrophic bacteria of the Thiobacillus-Ferrobacillus group. These ubiquitous organisms enhance metal leaching, and general aspects of heap leaching are discussed by Malouf, Trudinger, Pings, and Duncan et al. Conclusions and Recommendations Returning to the primary objective, how to reduce the mine drainage impact and recover metal values, we need to consider how the data may suggest avenues toward this objective. Boyles, et al., considered various

Jan 1, 1977

By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and &apos; steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation&apos; concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.&apos; Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

By R. D. Vaughn

The analysis of laminar flow of power-law non-Newtonian fluids in narrow, eccentric annuli is employed in this paper to discuss the problems of lubricant flow in journa! bearings and of errors introduced by eccentricity in experimental studies with concentric annuli on extruders and wellbore annuli. The velocity profile and pressure loss-flow rate equations are developed for the laminar flow region. In addition, the expected error in flow rate and pressure-loss measurements for concentric annuli as a result of eccentricity is determined. For example, a 10 per cent displacement of the core of an almost concentric annul us would cause a 1.8 per cent decrease in the observed pressure loss for a fluid with a power-law exponent n of 0.25. The corresponding increase in the observed volumetric flow rate would be 7. 5 per cent. INTRODUCTION Non-Newtonianism and eccentricity occur simultaneously in two engineering problems: (1) flow of lubricants in journal-bearings and pressure-reducing bushings, and (2) flow of non-Newtonian fluids in plastic extruders and wellbore annuli. The lubricants used for moving parts are often non-Newtonian in character — often they are plastic in behavior. A solution to the problem of flow of non-Newtonian fluids in narrow eccentric annuli is particularly pertinent to this problem. In all experimental studies of laminar flow of fluids in concentric annuli, such as in extruders and well casings, the error due to eccentricity must be estimated or studied. A number of publicationsl-4,6,7 have dealt with this problem for Newtonian fluids; however, I am not aware of work for non-Newtonian fluids. This work is directed to the non-Newtonian problem. Before the solution to the problem is given, the pertinent conclusions from the work on Newtonian fluids will be reviewed. Heyda 1 and Redberger and Charles 2 have published general solutions to the problem of the laminar flow of Newtonian fluids in eccentric annuli, apparently without knowing of the earlier work of Ca ld well 3 and Bairstow and Berry,4 which is reported by Dryden, et al. 5 Although several mathematical routes are encompassed by the work of these authors, the results appear to be equivalent. Redberger and Charles2 show that the error caused by eccentricity in concentric annuli is negligible for small diameter ratios (k < 0.5); however, for large diameter ratios (k + l), the error in the predicted flow rate can be as great as 100 per cent or more. Partial solutions to the problem are available from the work of Dryden,5 Tao and Donovan6 and Piercy, et a1.7 Tao and Donovan examined the case of flow in narrow, eccentric annuli (k + 1) with and without rotation of the annular core. These authors also reviewed previous work on this subject and verified their approach with experimental data. Dryden gives the solution for the limiting case of complete eccentricity or tangency. Piercy, et a l. published an early solution to the problem of narrow eccentric annular flow. The conclusions of Redberger and Charles2 and the experimental proof of Tao and Donovan6 both suggest that the region of large diameter ratios (k + 1) is of main interest and that the parallel planes approximation to the solution in this region is satisfactory. This method will now be extended to the laminar flow of non-Newtonian fluids in narrow eccentric annuli. THEORETICAL SOLUTION The geometrical aspects of the problem are illustrated in Fig. 1. To represent the non-Newtonian fluid the power-law model was selected. This model has many disadvantages which have been pointed out; nevertheless, its simplicity, its frequent and wide applicability justify its use in this work. Fredrickson and Bird8 and Savins9 have used it as a basis for a theoretical study of laminar flow of non-Newtonian fluids in concentric annuli.

Jan 1, 1966

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.&apos;&apos;&apos; At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-&apos;&apos; of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun&apos;s&apos;&apos; most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster&apos; proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer&apos;s knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen&apos;s bridge&apos;) was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer&apos;s knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen&apos;s bridge&apos;) was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

By L. A. Schrider, J. A. Wasson

A method of predicting waterflood performance has been developed that combines certain facets of several previously published prediction techniques. The manner of combination has required the development and use of some new and some little-known relationships and has eliminated several of the weaker assumptions inherent in the original individual prediction methods. This approach, which was designed for computer solution, has removed the necessity of referring to plotted curves and permits the analytical prediction of water flood performance for a five-spot well pattern in either homogeneous or stratified reservoirs. The Predicted values are expressed in common oilfield units rather than in abstract or dimensionless terms. The calculation procedure has been programmed in FORTRAN IV and the entire program listing is available to potential users.* Introduction Prior to initiation of secondary recovery of oil by waterflooding, the possibilities of economic success or failure must be evaluated with the greatest practical accuracy. Although many prediction techniques are available, most, if not all, have serious limitations. In recent years, the Bureau of Mines has attempted to stimulate interest in the secondary recovery of oil from Appalachian pressure-depleted reservoirs. Waterflooding, because of its widespread acceptance and success, is the principal secondary-recovery method considered. During the life of the project, several performance prediction methods have been studied and applied. Because these methods, individually, have inherent assumptions and limi-tations, portions of some of them have been selected and combined in an effort to eliminate such shortcomings wherever possible. We believe that the resulting technique is as accurate as the necessary available data will permit and that it has several distinct advantages over previously published methods. Development of the Method The fractional flow equation developed by Buckley and Leverett&apos; from Darcy&apos;s law is the fundamental mathematical statement describing immiscible fluid-fluid displacement in porous media. A generalized form of this relationship, whose derivation is readily available in the literature, is The formation dip, a, is usually very small in those petroleum reservoirs being considered for pattern waterflooding in the Appalachian area. Therefore. in many cases. a has an almist negligible value. In addition, Ap, the difference between the density of water and the density of oil, is relatively small. For these reasons the gravitational term may often be neglected. Capillary pressure is a function of saturation, which is in turn a function of distance from the upstream boundary of the system or the injection well. In this study it is assumed that the frontal zone of the waterflooding (or zone of capillarity) has negligible length and that only those saturations in the water-swept zone at breakthrough and later are of interest. As the distance in a waterflood pattern is comparatively large and the change in water saturation with distance is usually small, the change in capillary pressure with distance is negligible. The simplified form of the fractional flow equation is appropriate, therefore, in this application. Three variables must be considered in determining that fraction of the total fluid flow that consists of water: the viscosity ratio, saturation, and relative permeability ratio.

Jan 1, 1969

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH&apos;S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.&apos; The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By F. W. Smith

Within the Northern Pennine Orefield, England, intersections of fluorite veins are generally richest in ore, and their recognition enables investigation of the ore potential of the intersecting bodies. A method, based on routine analysis of fluorite for yttrium, has been used with success in mines of the district to predict the location of intersections in partially developed fluorite-bearing ore bodies. This short note is intended as a brief introduction; the details of United Kingdom applications are to be published at a later date. Geology The Northern Pennine Orefield is the second largest fluorspar-producing region in Britain. The associated minerals galena, sphalerite, chalcopyrite, barite, and witherite have all been extensively worked in the past but, with the exception of a single barytes mine, all of these operations are now abandoned. Galena alone is recovered as a byproduct of fluorspar beneficiation. At the present time two companies are producing about 38,000 tpy of fluorspar from high grade vein ore bodies, and a number of concerns are actively prospecting in old lead workings. The mineralization is localized in veins and replacement flats within favorable lithologies in an alternating limestone, sandstone, shale sequence. Since the thickness of individual beds is not great (generally less than 20 m), vein bodies tend to be ribbon-shaped, with length greatly exceeding width and height (Dunham). They thus present difficult exploration targets for conventional diamond drilling techniques. Ore grade varies greatly along the veins, which can change rapidly in character from mineral stained fault gouge to massive mineral bodies up to 10 m in width. It has been known for a very long time that the richer ore bodies tend to be associated with vein intersections in favorable beds. It is assumed that vein fissure intersections provided vertical channelways through which hot ore-bearing brines were able to ascend from deeper cavities in the sequence. Thus investigation of intersections at other horizons generally yields further ore bodies. Technique The relative concentration of yttrium in fluorite is a good indicator, in the North Pennines, of the direction of flow of mineralizing fluids. In all of the ore bodies so far studied in detail in this region, the concentration of yttrium increases markedly in the direction of vein intersections that are believed to have acted as feeder zones to the remainder of the bodies. The reason for this relationship is probably connected with the degradation of soluble rare earths-fluoride complexes by the changes in various physicochemical parameters of the hydrothermal fluids as they entered the ore body cavities from the feeder zones. The simultaneous release of free fluoride ions also contributed to the increased ore values in these intersection zones. Yttrium values in fluorite taken from a longitudinal traverse of the western ore body, Redburn mine, Rookhope, are plotted in [Fig. 1.] The position of a major vein branch and three cross veins are clearly indicated by yttrium maxima. The cross veins themselves contain up to 2.5 m of low grade fluorspar ore. The exact positions of B and C were unknown previous to the geochemical survey. Similar results have been obtained for several other veins and ore bodies in the area. Clean fluorspar was collected as bulk samples from within 300 mm of the vein wall and, since the vein infilling is simple, with mineral growth from the walls inward, analyses of the samples are considered comparable along the length of the ore body. A number of samples taken from the center of the vein show a

Jan 1, 1975

By J. H. Swislzer

TWO-LIQUID miscibility gaps have been found to exist in both the CaO-SiO, system above 1705 and the Cr,03 system above 2200"c. Glasser and 0sborn3 studied the extension of these miscibility gaps into the Ca0-Si0,-Crz03 ternary system and reported that the two-liquid region is not present at temperatures below the monotectic temperature of 1705°C in the CaO-SiO, system. The present authors, in connection with other work on surface-tension measurements and foam stabilities in the same ternary system,4 observed that the miscibility gap exists at temperatures as low as 1600°C. A brief experimental study was devoted to deter- mining tie-line positions in the two-phase region. The technique used was to obtain a separation of phases at 1600°C, then to quench-in the high-temperature phases and obtain a chemical analysis of each phase. It was necessary to take special precautions in obtaining a phase separation because of a tendency toward emulsification of the two liquids. The procedure followed is described in the schematic drawing in Fig. 1. A small platinum crucible containing several pinholes on its sides was placed inside a larger platinum crucible. An excess of Crz03 was placed in the outer crucible, together with a prefused binary CaO-Si02 mixture, and the Cr203 was allowed to diffuse through the pinholes and saturate the same binary CaO-SiOl mixture in the smaller crucible. After equilibration at 1600°C, the inner crucible contained only the lighter liquid (liquid A) saturated with Cr203. The outer crucible contained layers of both liquids. Experimental data were obtained by analyzing the entire contents of the inner crucible and only the bottom layer of the larger crucible (liquid B). The upper layer of the outer crucible was not suitable for chemical-analysis purposes because dispersions of the second phase sometimes were found in the samples. The technique is described in more detail in Ref. 4. The same method was used by Grieveson and urkdoan&apos; to study a miscibility gap in sulfate-ferrite melts, where the liquids were difficult to separate because of similarities in density. In addition to the phase-separation experiments, a few others were conducted to obtain information

Jan 1, 1964