Search Documents

By H. Brevers, Maurice Rey

Through circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. Flotation of Realgar Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arseno-pyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed non-polar and the other polar, a distinction that has been stressed in a previous paper.' Depression of Realgar and Flotation of Cinnabar Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1943

By Maurice Rey, H. Brevers

Through circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. Flotation of Realgar Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arseno-pyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed non-polar and the other polar, a distinction that has been stressed in a previous paper.' Depression of Realgar and Flotation of Cinnabar Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1943

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;' it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;' it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By G. A. Colligan, G. L. F. Powell

A new experimental technique has been developed to study nucleation behavior in eutectic alloys. It is somewhat similar to that applied by Sundquist and Mondolfo1 but with the advantages that: 1) bulk samples are undercooled instead of small droplets thus allowing the thermal behavior to be monitored by a thermocouple immersed in the sample, and 2) nucleation behavior is investigated in the same sample on either side of the eutectic composition by adding additional component to the sample under controlled conditions which preclude the addition of nu-cleation contaminants. Sundquist and Mondolfo carried out ]nucleation ex-periments on a large number of eutectic alloy sys-tems and concluded that nonreciprocal nucleation operated. If one phase a was a good nucleant for the other phase 0, then B was a poor nucleant for a. This was determined experinlentally by comparing the nucleation temperatures of 100 to 300 u diameter droplets of hypereutectic and hypoeutectic composition cooled from above the liquidus and from a temperature between the liquidus and the eutectic temperature. Primary phase a was concluded to be an efficient nucleant for the other phase B, if the following experimental result was obtained. Referring to Fig. 1, the temperature TI at which a drop of hypereutectic alloy of composition B froze when cooled from above the B liquidus was noted. This was the nucleation temperature for B in the absence of a. A drop of hypoeutectic alloy of composition A was then frozen from temperature T2 between the a liquidus and the eutectic temperature. The temperature T3 at which the eutectic nucleated in the presence of the primary or proeutec-tic a was noted. If this temperature T3 was higher than the temperature TI at which the B nucleated in a hypereutectic alloy, it was concluded that the primary a had nucleated the 6. This temperature T3, representing a certain undercooling below the equilibrium eutectic temperature Te , was designated ?TB by a> the undercooling below T, for nucleation of 13 by a. If there was no substantial difference in nucleation temperature between the hypereutectic drop cooled from above the /3 liquidus and the hypo-eutectic drop cooled from a temperature between the a liquidus and the eutectic temperature, it was considered that the a nucleated B at an undercooling equal to or greater than that at which P nucleated from a hypereutectic alloy. Sundquist and Mondolfo1 found that faceted primary crystals were good nucle-ants for metals that grow as orthogonal dendrites when present as the primary phase. Jackson2 has questioned Sundquist and Mondolfo's technique and proposed that in Sundquist and Mon-dolfo's samples, such as composition A, primary a retained B in reentrant grooves at their surfaces when heated to a temperature above the eutectic but below the a liquidus. This objection was suggested by experiments with organic eutectics where reten-

Jan 1, 1970

By B. L. Averbach

THE rolling process may be considered as a case of a nonhomogeneous plastic flow. In such a heterogeneous deformation there is no direct general solution, and the plastic deformation varies from point to point as a function of the coordinates. It is practicable to determine these plastic strains only at the conclusion of the rolling process, and the local strains can be studied by observing the deformations produced in a suitably placed grid system. Strains at the surface of a bar after rolling have been reported by MacGregor and Coffin,' but the strain distributions within the bar have not been previously observed. Siebel² has investigated the plastic deformations resulting from wire-drawing by splitting the wire along its axis, milling a grid coordinate system on the inner plane surfaces, and binding the .wire together so that it would pull through a die as a single unit. This method was possible because of the rotational symmetry of the die. In the rolling process, however, such a system was not readily applicable. This paper describes another method of including a grid system, and reports some preliminary data on the plastic rolling strains within a square bar. Experimental Procedure 2.1 mm wide (144 network squares per sq in.) was punched from a thin lead sheet with a steel die and supported in a brass mold by thin copper wires. Pure tin was then poured around the grid to form a solid bar, with the network securely imbedded at. a given position. This bar was then machined to a square 15.2 mm (0.60 in.) wide, and then radiographed. The lead grid was quite adherent and sufficiently ductile to follow the deformation of the bar faithfully. The network lines also remained sharp enough to maintain a high radiographic contrast, and the tin bar, with the grid included, could withstand considerable deformation at room temperature without splitting at the interface. In order to fill the mold, it was necessary to cast the tin at 260-280°C and during pouring the lead grid was supported at short intervals to prevent warping. Some shrinkage cavities were encountered, but only bars which were free of shrinkage in the network region were used. This method is similar to the one employed by Steinberg" in an investigation of the strain distribution in a tensile specimen. Before rolling, the machined bars were radiographed in two directions to obtain accurate initial dimensions of each square and to observe whether the grid was straight and correctly positioned. The rolling was performed in a small hand mill with 2 in. diam rolls at room temperature, and a 20 pct reduction based on the original height was employed. The rolls were clean and no lubricant was used. Halfway through the bar, at the center of the network, the rolls were reversed and the bar extracted. These bars were then radiographed again

Jan 1, 1951

By J. J. Gilman

THEORIES of fracture in metals have been based primarily on the dependence of fracture strength on grain size. This dependence was first observed by Masing and Polanyi.l These workers, as well as 0rowan12 and Davidenkov and Wittman,' thought the grain size could be equated with the crack size in the Griffith condition for crack propagation.4 In this way they could account for the observed proportionality between fracture stress and the reciprocal square root of the grain size. The chief results of recent investigations of the fracture strength of polycrystals are summarized in Fig. 1. Low for iron,5 Petch for iron,' Greenwood and Quarrel for zinc, Petch and Zein for zinc,' and Hauser, Landon, and Dorn for magnesium'' have all found that the fracture stress of a polycrystal is proportional to the reciprocal square root of the grain size. Also, they find that, for large grain sizes, the fracture stress lies near the extrapolation of the yield-stress curve determined at small grain sizes; where measurable plastic strain precedes fracture. Low9 has gone a step further and shown that, in Range 1, the fracture stress in tension is almost identical to the yield stress in compression for a given grain size. Homes and Gouzou, 10 and Low also have shown that, in Range 2 of Fig. 1, microcracks form when the yield stress is reached, but they do not cause failure until the stress reaches a much higher value. The fact that yielding always precedes fracture suggests that fracture is induced by plastic flow. A mechanism by which this might occur was first proposed by Zener.11 He pointed out that blocked dislocations would cause stress concentrations which might cause fracture. The blocking would be caused by grain boundaries. This idea has been developed by Eshelby, Frank, and Nabarro,12 by Koehler,13 and by Stroh.14 By means of etchpits blocked dislocations have been observed in brass by Jacquet,15 in zinc by Gilman,16 and in lithium fluoride by Gilman and johnston. The blocked-dislocation theory and the experiments that bear on it have been summarized by Mott.18 One of the strong points of the blocked-dislocation theory is that it can explain the grain-size dependence of the fracture stress in a natural way. However, Low9 has pointed out that the theory is not satisfying when it is considered quantitatively. Gilman10 also has criticized the theory and presented an alternative interpretation of the relation between fracture stress and grain size. Since the blocked-dislocation theory is not the only theory that can explain in the grain-size effect, it is necessary to find other evidence either to support or deny it. In this investigation the following points were studied: 1) If blocked dislocations normally cause fracture, then the fracture stress ought to be very high in the absence of plastic glide. Is it? 2) If dislocations must be blocked in order for metals to fracture, then certain types of grain

Jan 1, 1959

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By C. O. Bundranl, Peter Dehlinger, W. H. Browne

Brief laboratory investigations are described which attempt to determine optimum .sand concentrations in gel-sand and oil-sand1 well-treatments. The investigations apply to the case where sand acts as a propping agent in formation fractures. Both analytically and experimentally it is demonstrated that optimum sand concentrations can be defined. It is difficult to translate laboratory results to field treatments, however, since the relative distribution of sand and fluid in fractures may not be the same as injected. This is because fluid may penetrate the furtherest narrow portions of fractures, which would not pass sand. Optimum concentration of a monolayer of Ottawa sand in fractures of 0.025-in. width at the usual range of pressures encountered in treatments appears to be about 95 to 2 lb/gal. of gel. An investigation of abrasion of rock-walls by sand in treatments, described in the Appendix, shows that such abrasion is not probable in significant amounts. INTRODUCTION Experience in the Spraberry formation of West Texas, as well as in other formations, has shown that. sand is a necessary and vital part of gel-sand and oil-sand treatments. Many observers of treatments have also concluded that there seems to be an optimum range of sand concentration for these injections. Brief laboratory investigations were made at Battelle Memorial Institute to study flow in fractures with different sand concen- trations. To investigate the existence and range of optimum concentrations in the laboratory, however, necessitates knowledge of the mechanism by which the sand aids in increasing subsequent production. The action of sand in fractures is usually thought to be either that of a propping agent, thus providing a greater effective formation permeability; that of an abrasive in eroding fill material in fractures; or that of an abrasive eroding rock-wall irregularities along fracture surfaces. Investigations described in the Appendix show that sand does not appear to erode rock-wall materials appreciably. In a subsequent paper it is reasoned, at least for the Spraberry formation of West Texas, that the primary action of sand is not in removing fill materials in fractures. In this formation, and probably others, too, the main effect of sand appears to be that of a propping agent. Both analytical and experimental investigations were made for the case of a monolayer of sand acting as a propper, in which sand concentrations were determined that would, after treatment, permit flow of the maximum quantities of oil from the formation into a well. If too few sand grains are injected into fractures in which the bottom hole pressure has decreased appreciably below the original formation pressure, the confining pressure in the formation may become relatively large, thus compress the rock-walls around the sand grains, essentially close fractures, and so decrease the subsequent flow of oil. Similarly, if too much sand is used, the flow of oil will he impeded by the volume of sand present. THEORY Although an analytical approach to determining optimum sand concentrations involves gross assumptions.

Jan 1, 1955

By H. W. Schadler

Single crystals of tungsten, which were grown by electron bombardment floating zone refining, were strained 2 pet in tension and bending at 298°, 77°, and 20°K to determine the modes and crystallography of the plastic deformation of these temperatures. At 77° and 20°K plastic deformation occurs by slip on systems of the type (011) [111] and by twinning on (112)-type planes. For crystals strained at 298°K, deformation occurs by slip in [111] directions on either (Oil)- or (112)-type planes. CURRENT models for the initiation of brittle fracture in crystalline materials are based on a knowledge of the details of their plastic deformation.1 Body-centered cubic tungsten exhibits brittle failure at temperatures below about 500 °K yet the modes and crystallography of its plastic deformation have not been studied below 1000°K. In 1924, Goucher2 reported that tungsten single crystals with a total impurity content of less than 0.01 wt pet deformed by slip on the (112) [111] system in the temperature range 1000° to 3000°K. He also observed (001) [010] slip in one crystal which was constrained by the presence of a large fissure. According to Barrett3 tungsten also deforms by twinning on the (112) plane in the [111] direction, but he gives no details on the tendency for twin formation or the temperature range in which twinning occurs. Therefore, as a necessary part of a study of the factors influencing the brittle fracture of tungsten, the modes and crystallography of the plastic deformation were determined at 298°, 77°, and 20°K. Tungsten single crystals, grown using the electron-bombardment zone-refining technique first described by Calverly,4 were deformed to between 1 and 2 pet plastic strain in tension and bending. The surface offset resulting from slip or twinning was observed with an optical microscope to determine the crystallography of the deformation. The existence of twins was proven by the standard polishing and etching technique; and the crystallography of dislocation motion was followed using the dislocation etchant described by Wolff.5 Some observations on the fracture characteristics of tungsten single crystals are included. EXPERIMENTAL TECHNIQUES Growth, Purity, and Perfection of the Crystals-Several years ago Calverly, Davis, and Lever4 dem-onstrated the feasibility of growing tungsten single crystals by the electron-bombardment floating zone-refining technique, and Carlson6 showed that crystals produced in this way had a high degree of purity and were ductile at room temperature. Tungsten single crystals produced by this technique in equipment similar to that described by Carlson were used in this study. The starting material, a powder metallurgy product, was obtained in the form of a swaged 1/8-in. rod from the General Electric Wire Plant in Cleveland, Ohio. The crystals were grown from this material in a vacuum of 10"4 mm of Hg by passing a molten zone 1/8 in. long down the rod twice at a speed of 3 mm per min. At this zone speed

Jan 1, 1961

By L. L. McMurray

ILMENITE is the most important raw material for manufacture of titanium dioxide.1 Industrially, several other products are made from ilmenite, the most important of which are: ferrotitanium, ferro carbon-titanium, copper-titanium, titanium carbide and titanium nitride. The production of titanium metal is still in the laboratory stage because of the difficulty of extraction and as yet no important application for the metal has been found. Ilmenite has received considerable attention as an industrial raw material. Imports of ilmenite concentrates for the first nine months of 1941 were 156,737 short tons, the chief source being Travancore, India.2 Domestic production of ilmenite has here-tofore been confined to Amherst and Nelson Counties, Virginia, where a complex rutile, ilmenite, and apatite ore is mined and treated to utilize all three of these minerals. A recent report3 has described development of the large titaniferous magnetite ore body at Tahawas, New York, where it is expected that 800 tons of ilmenite concentrates, containing 48 per cent Ti02 will be produced daily. Additional domestic production is expected from a large ilmenite deposit recently opened in Caldwell County, North Carolina. Flotation tests indicate that a high-grade concentrate containing 53 per cent Ti02 can be made from the North Carolina ore. Prospecting of domestic ores in other areas has been reported.4 It appears that increased domestic production of ilmenite may well save considerable shipping space so vitally needed in these times. The composition and chemical structure of pure ilmenite is given by Dana as: FeO, TiO2; Ti, 31.6 per cent, Fe, 36.8 per cent, 02, 31.6 per cent. This composition is variable in that some iron or titanium may be replaced, giving a variable iron-titanium ratio. As an example, the iron-titanium weight ratio of ilmenite in Caldwell County, North Carolina, has been determined to be 0.94 (using 97.1 per cent ilmenite concentrate obtained by heavy liquids on minus 150-mesh ore) compared with theoretical 1.16. No rutile was noted in this ore to account for the low value. This North Carolina ore is free of magnetite, which is a common associate of ilmenite ores. In view of a large potential production from North Carolina, the Tennessee Valley Authority conducted a study of methods of concentration of that ore, of which the results are reported herein. THE ORE Five samples of ore were taken from the deposit at various exposed locations and were mixed for the study and testing. An attempt was made to proportion the amount of weathered and unweathered portions in making the composite sample, so as to approximate actual operating conditions. An examination of representative specimens of the sample showed the following general facts: I. The black mineral comprising nearly 70 per cent of the ore is ilmenite.

Jan 1, 1944

By K. L. Moazed, G. M. Pound

An investigation was made of the deposition of silver from a thermal beam onto tungsten field-emitter tips at 300°K. "Island"-type nuclei were observed to form and grow. The nucleation of silver crystals occurs preferentially on non-close -packed planes of a tungsten tip at a critical volume free-energy change of about —2900 cal per cc. The adatom population which is critical for appreciable nucleation rate of silver crystals is about 0.2 of a monolayer and is essentially independent of beam flux, time, and source temperature. This result is strong evidence that a metastable equilibrium exists between adatoms and critical nuclei, as assumed in the present theory. SOME of the more significant studies of nucleation in deposition of metals from vapor beams have been conducted by measuring the thermal beam flux which is critical for appreciable rate of nucleation on a substrate surface held at a given temperature.'2 The observed critical supersaturations may be described in terms of Eq. [7] which was derived3'3a on the model of an adsorption, surface migration, and statistical fluctuation mechanism. However there usually made with a low-power optical microscope, a fairly insensitive method of detection. The object of the present study was to overcome some of these difficulties by measuring the critical supersaturation for condensation of a thermal beam of silver onto a tungsten field-emitter tip. Such a tip may be cleaned by electrically heating it to a high temperature in situ, and the high vacuum obtainable in a field-emission tube (10-10 torr) precludes adsorption of residual gases for convenient periods of time. Furthermore, the degree of cleanliness, the orientation, and the state of imperfection of the tip may be ascertained from the field-emission pattern. Detailed explanations of theoretical considerations and experimental procedures relating to the field-emission microscope may be found in a number of excellent review articles12'13 and thus only a brief description will be given here. The electronic work function of a metal is defined as the energy that an electron needs to escape from the potential field of the solid. By applying a large field between the surface of the solid and a suitable collector, it is possible to free the electrons by the tunnel effect. Fields of approximately 30 million v per cm are needed to produce this effect, and such fields are obtained in practice by using microscopic surfaces of high curvature (tips). Because the work function of a metal is a function of surface orientation, the emission from the various planes is different, and thus it is possible to obtain a representation of the surface in the emission microscope. In general, the work function is higher for the more densely packed planes. Fig. 1 shows a pattern for "clean" tungsten in which the central dark region represents the (110)

Jan 1, 1964

By Maurice Rey, H. Beavers

THROUGH circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper.1 DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR 'Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By Maurice Rey, H. Brevers

THROUGH circumstances connected with the war, the senior author lost his records therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH- of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper. DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By L. L. McMurray

Ilmenite is the most important raw material for manufacture of titanium dioxide.' Industrially, several other products are made from ilmenite, the most important of which are: ferro titanium, ferro carbon-titanium, copper-titanium, titanium carbide and titanium nitride. The production of titanium metal is still in the laboratory stage because of the difficulty of extraction and as yet no important application for the metal has been found. Ilmenite has received considerable attention as an industrial raw material. Imports of ilmenite concentrates for the first nine months of 1941 were 156,737 short tons, the chief source being Travancore, India.2 Domestic produttion of ilmenite has heretofore been confined to Amherst and Nelson Counties, Virginia, where a complex rutile, ilmenite, and apatite ore is mined and treated to utilize all three of these minerals. A recent report3 has described development of the large titaniferous magnetite ore body at Tahawas, New York, where it is expected that 800 tons of ilmenite concentrates, containing 48 per cent TiO2 will be produced daily. Additional domestic production is expected from a large ilmenite deposit recently opened in caldwell county, North carolina. Flotation tests indicate that a high-grade concentrate containing 53 per cent TiO2 can be made from the North Carolina ore. Prospecting of domestic ores in other areas has been reported.' It appears that increased domestic production of ilmenite may well save considerable shipping space so vitally needed in these times. The composition and chemical structure of pure ilmenite is given by Dana as: FeO, TiO2; Ti, 31.6 per cent, Fe, 36.8 per cent, O2, 31.6 per cent. This composition is variable in that some iron or titanium may be replaced, giving a variable iron-titanium ratio. As an example, the iron-titanium weight ratio of ilmenite in Caldwell County, North Carolina, has been determined to be 0.94 (using 97.1 per cent ilmenite concentrate obtained by heavy liquids on minus Iso-mesh ore) compared with theoretical 1.16. No rutile was noted in this ore to account for the low value. This North Carolina ore is free of magnetite, which is a common associate of ilmenite ores. In view of a large potential production from North Carolina, the Tennessee Valley Authority conducted a study of methods of concentration of that ore, of which the results are reported herein. The Ore Five samples of Ore were taken from the deposit at various exposed locations and were mixed for the study and testing. An attempt was made to proportion the amount of weathered and unweathered portions in making the composite sample, so as to approximate actual operating conditions. An examination of representative specimens of the sample showed the following general facts: 1. The black mineral comprising nearly 70 per cent of the ore is ilmenite.

Jan 1, 1948

By B. L. Averbach, M. Cohen, G. P. Conard

IT has been frequently observed that, when metal crystals are bent and annealed or when they are bent at elevated temperatures, the asterism of the Laue spots is split discontinuously into tiny intensity maxima. This finding indicates that segmented crystallites or subgrains are produced, which are relatively undistorted within themselves but which differ slightly in orientation from their neighbors. The following viewpoints have been put forward concerning the nature of this segmentation process: 1—Crussard' has described the phenomenon as "re-crystallization in situ." According to this mechanism, the deformed lattice recrystallizes on heating into an aggregate of comparatively strain-free subgrains separated from one another by low-angle boundaries and having nearly the same orientation as the original crystal. This process differs from the classical type of recrystallization in that the latter involves the formation of grains having quite different orientations from that of the mother crystal. 2—A similar but more detailed picture has been advanced by Cahn' who adopted the term "polygonization." In this interpretation, the plastic bending of lattice planes results in an excess of dislocations of one sign, but at suitable temperatures these dislocations migrate along slip planes and collect in localized regions to form an array of low-angle boundaries. Concurrently, the lattice segments between the boundaries lose their curvature and elastic strain. 3—The "cell formation" concept of Wood and co-workers: unlike the two hypotheses cited, postulates that the segmentation of the lattice is basically a mode of deformation and is not an annealing phenomenon. Cell formation appears to compete more effectively with respect to the normal slip process as the deformation temperature is increased and as the strain rate is decreased. The present work was performed on 3.2 mm diameter 99.99' pct Zn single crystals, grown from the melt in a gradient furnace. The major impurity was 0.003 pct Fe. The crystal orientations ranged from those with basal plane parallel to the rod axis to those with the basal plane almost perpendicular to the rod axis. The specimens were bent on templates to effective radii varying from 14.2 to 1.3 cm at the temperatures from —196" to 100°C. In each case, the axis of bending was parallel to the basal plane. Subsequent annealing was carried out at temperatures from —196" to 400°C. Back-reflection Laue pictures were taken on the convex surface of the bent specimens, before and after annealing. This procedure was found to yield better resolution of the detail in the diffraction spots than did the previously used Laue transmission technique. Some X-ray pictures of rods bent at —196" and —78°C were taken at these respective temperatures without intermediate warming to room temperature. In addition, bent crystals were acid cut" parallel to the basal plane, and double-crystal spectrometer rocking-curves were obtained from the etched (0001) face before and after increment an-

Jan 1, 1954

By L. L. McMurray

Ilmenite is the most important raw material for manufacture of titanium dioxide.' Industrially, several other products are made from ilmenite, the most important of which are: ferro titanium, ferro carbon-titanium, copper-titanium, titanium carbide and titanium nitride. The production of titanium metal is still in the laboratory stage because of the difficulty of extraction and as yet no important application for the metal has been found. Ilmenite has received considerable attention as an industrial raw material. Imports of ilmenite concentrates for the first nine months of 1941 were 156,737 short tons, the chief source being Travancore, India.2 Domestic produttion of ilmenite has heretofore been confined to Amherst and Nelson Counties, Virginia, where a complex rutile, ilmenite, and apatite ore is mined and treated to utilize all three of these minerals. A recent report3 has described development of the large titaniferous magnetite ore body at Tahawas, New York, where it is expected that 800 tons of ilmenite concentrates, containing 48 per cent TiO2 will be produced daily. Additional domestic production is expected from a large ilmenite deposit recently opened in caldwell county, North carolina. Flotation tests indicate that a high-grade concentrate containing 53 per cent TiO2 can be made from the North Carolina ore. Prospecting of domestic ores in other areas has been reported.' It appears that increased domestic production of ilmenite may well save considerable shipping space so vitally needed in these times. The composition and chemical structure of pure ilmenite is given by Dana as: FeO, TiO2; Ti, 31.6 per cent, Fe, 36.8 per cent, O2, 31.6 per cent. This composition is variable in that some iron or titanium may be replaced, giving a variable iron-titanium ratio. As an example, the iron-titanium weight ratio of ilmenite in Caldwell County, North Carolina, has been determined to be 0.94 (using 97.1 per cent ilmenite concentrate obtained by heavy liquids on minus Iso-mesh ore) compared with theoretical 1.16. No rutile was noted in this ore to account for the low value. This North Carolina ore is free of magnetite, which is a common associate of ilmenite ores. In view of a large potential production from North Carolina, the Tennessee Valley Authority conducted a study of methods of concentration of that ore, of which the results are reported herein. The Ore Five samples of Ore were taken from the deposit at various exposed locations and were mixed for the study and testing. An attempt was made to proportion the amount of weathered and unweathered portions in making the composite sample, so as to approximate actual operating conditions. An examination of representative specimens of the sample showed the following general facts: 1. The black mineral comprising nearly 70 per cent of the ore is ilmenite.

Jan 1, 1948