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By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Walter R. Hibbard, George H. Eichelman, William P. Saunders

INTEREST in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,1 has resulted in the application of similar heat treatments to other eutectoid transformations. Studies2.3.4 of the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5,6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported' as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. PREPARATION OF ALLOYS The copper-silicon alloy equilibrium diagram is shown in Fig I. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutectoid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct). Smith5 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.7 Following the casting techniques of Krynitsky, Saunders and Stern,8 the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under the melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X ¾ in., was annealed at 750°C for 21 brand furnace cooled. About 1/16 in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. methods.9 The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1948

By C. G. Dunn

Nuclei that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,&apos; that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclasses† of the 36 third-order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of deformation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a (110) plane in a <100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is not particularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1947

By C. G. Dunn

Nuclei that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,&apos; that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclasses† of the 36 third-order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of deformation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a (110) plane in a <100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is not particularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1947

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4&apos;C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Torgrim Eftestoel, Leif Olsen, Ove Sandberg

IN the vertical contact Soederberg electrode for aluminum furnaces more or less serious cracks are sometimes formed in the electrode, with harmful effect on furnace operation. The problem of crack formation has been studied on a laboratory scale to obtain a better understanding of this phenomenon. The primary cause of crack formation is the shrinkage of the electrode carbon, which is opposed by the normal thermal expansion of the steel contact studs. The forces thus set up are active in the temperature interval from which the electrode obtains a rigid structure (450" to 500°C) to furnace operational temperature (950°C). A visualization of our reasoning is given in Fig. 1, which shows the different behavior of mild steel and electrode carbon during baking. Research work performed to determine relationships between crack formation and shrinkage will be described. A brief description of the method developed for measurement of shrinkage will be given, as well as a critical analysis of this method. Also, raw material quality and paste composition variables will be related to shrinkage phenomena. Laboratory Test of Crack. Formation To test the tendency toward crack formations of Soederberg electrodes from different pastes, experiments were performed to simulate conditions of actual commercial electrodes, and are described as follows. A cylindrical test electrode is prepared by tamping the electrode paste to be examined in a sheet iron casing, 350 mm diam by 700 mm height. The casing is perforated, with the holes (2 mm diam) 50 mm apart, to facilitate the escape of volatile matter during baking. A cylindrical steel stud of actual service size, 100 mm diam, is welded eccentrically to the bottom steel plate, and protrudes up through the paste. During baking, a crack may thus occur in the weaker part of the test electrode. The electrode is baked by lowering the assembly slowly into an electric furnace, the temperature of which is kept constant at 900°C. After baking of the electrode, the sheet iron casing is removed and the electrode inspected for cracks. The pictures in Fig. 2 are of three different pastes baked according to the present method. Electrode 1 has a large crack; electrode 2, a somewhat smaller one; and electrode 3, only a minor crack. As will be seen from the simplified sieve analysis diagram of Fig. 2, the compositions of the pastes in question are very different. This subject will be discussed later in greater detail. Crack Formation and Shrinkage Relationships It is well known that shrinkage occurs in coke in the higher temperature ranges of coal

Jan 1, 1958

By G. C. Gambs

The electric utility industry is the largest customer of the coal industry and consumes nearly 50% of the present coal production in the United States. The byproduct of the burning of coal in utilities is ash in several forms including fly ash, bottom ash and bottom slag. At present, very little of the coal ash produced is being used and must be disposed of as waste. The coal industry should look upon this waste material as a valuable by-product which, if it can be sold for $2 to $4 per ton, will have the net effect of reducing the cost of coal to the utility by 1¢ to 2¢ per million Btu. There are many ways to use coal ash and thus benefit both the coal industry and the electric utility industry by reducing the cost of coal as burned. The solutions to the problems are obvious and all we have to do is apply them. The electric utility industry is the largest customer of the United States coal industry, consuming nearly 50% of present coal production. By 1980, the electric utilities are expected to burn over 500 million tpy of coal or 75% of total coal production. When coal is burned in electric utility plants, ash is produced in one of several forms. These include fly ash, bottom ash and bottom slag. At the present time, approximately 20 million tons of these ashes are produced and must be disposed of by the utilities at a cost of 50¢ to $2 per ton. In 15 years, more than double this quantity will be produced. Only a small quantity of this ash is put to any practical use. Much remains to be done about expanding uses for fly ash and bottom slag. It is well known that fly ash, when used to replace a portion of the cement in a concrete mix, will produce highest quality concrete. The Corps of Engineers and the Bureau of Reclamation have constructed dams and other concrete structures for years with fly ash as a partial replacement for cement. However, many construction firms do not use it. This can become an opportunity for the coal industry to reduce the cost of coal delivered to utilities. Any fly ash, or other ash or slag, which is sold by the utilities, reduces the cost of coal burned by the utility. As much as 1¢ to 2¢ per million Btu could be taken from the fuel cost for each ton of ash sold which otherwise must be disposed of at a cost.

Jan 1, 1967

By A. S. Joy

Vacuum flotation tests carried out according to the method of Schuhmann and Prakash1 have shown that the acid limiting edge of the flotation area for a Brazilian hematite, in the presence of dodecylamine, is a straight line of slope approximately unity. The flotation tests and the structure, surface ionization, and electrokinetic properties of this hematite have been fully discussed elsewhere. 2 The numbers of adsorbed H+, and OH- ions and collector molecules have been determined in the range of critical conditions defining the acid limit of the flotation area. The total amine adsorption is shown in Fig. 1 as a set of contours superimposed on the straight part of the flotation area. These were determined by spectro-photometric estimation of the complex formed between residual amine and the anionic dye Orange II.3 The ionic strength of the solutions was kept constant and at a value in sufficient excess of the amine concentration to ensure that the diffuse part of the double layer was populated predominantly by indifferent ions. Adsorption of H+ and OH- in the absence of amine was found by potentiometric acid-base titration in the presence of hematite.4 The form of the adsorption-titration curves suggested that the hematite surface behaves in an amphoteric manner, and that positively charged sites arise through loss of a hydroxyl ion, and negatively charged sites by loss of a hydrogen ion. On this basis, curves 8 and 9, shown in Fig. 2, were calculated from the titration curves. These show the variation of the numbers of positive (s +) and negative (s—) sites with pH. To distinguish between ionic and other modes of adsorption, zeta-potential determinations have also been made using the streaming potential technique. The influence of amine on the zeta-potential of the mineral over a wide pH range is shown in Fig. 3. The change in charge ?s, due to adsorption of amine ions in the Stern layer, was calculated by applying the Gouy-Chapman theory, as modified by Stem, to the results shown in Fig. 3. The validity of this treatment has been shown by Ottewill and Jaycock.5 The three full lines, Nos. (1) through (3), included in Fig. 2 show the relationship between ?s and pH at three amine concentrations. The general conclusion from the zeta-potential curves is that adsorption of amine causes a reduction in the negative charge on the surface. Comparison of the values shown in curves (1) through (3) of Fig. 2 with the - curve shows that the magnitude of the reduction is comparable with that of s - at any given

Jan 1, 1964

By Gerald Edmunds

In a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the , origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical changc in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained—i.e., (001) parallel, ± 2oo, to the surface—as was obtained when it was cast against air, Transite or iron.&apos; Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about 1/4 in. of lead, then 1/2 in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 136 in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,&apos; with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two 1/4-in. diameter aluminum-alloy die-cast tensile bars and on a 1/8 by 1/2-in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. Summary A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. Acknowledgment The X-ray determinations were conducted by M. L. Fuller.

Jan 1, 1945

By A. E. Back, W. Wyman, K. E. Tame, S. F. Ravitz

In 1940, when it appeared that the United States soon might be cut off from foreign sources of high-grade manganese ore, the Bureau of Mines began an extensive series of investigations on the production of ferro-grade products from low-grade domestic ores by ore-dressing, pyrometal-lurgical, and hydrometallurgical methods. Among the hydrometallurgical processes for oxide ores investigated was a sulphur dioxide process in which the manganese was recovered from solution by precipitation with lime;&apos; this process is essentially as follows: The ground ore is suspended in water and leached with SO2 gas to extract the manganese as manganese sulphate. Calcium chloride is then added to the slurry to precipitate calcium sulphate and form manganous chloride solution, and the resultant slurry is filtered to remove the calcium sulphate together with the insoluble portion of the ore. Calcium hydroxide is added to the filtrate and the mixture is agitated with air to precipitate hydrated oxides of manganese and regenerate calcium chloride. The precipitate is calcined, and the calcium chloride is recycled. To determine manganese extraction, reagent consumption, grade of product, and similar data for this process, a labora- tory investigation was started. Two minor modifications in the process were soon made: (I) the ore was suspended in calcium chloride solution instead of in water in order to extract the manganese and precipitate the calcium sulphate in one step, and (2) the agitation with air after the addition of slaked lime to the filtrate was omitted because manganese hydroxide is readily precipitated without air agitation and can be nodulized or sintered to a satisfactory product. When the process was carried through a series of cyclic tests, it was noted that the concentration of dithionate ion (which is one of the products of oxidation of SO2 by MnO2) in the cycled solution gradually increased; at the same time the chloride content of the solution gradually decreased, owing to soluble losses in the leach residue and in the precipitate. After a number of cycles, the calcium chloride became virtually completely replaced by calcium dithionate, the quantity of dithionate ion formed during the leach being more than enough to make up for the losses of dithionate in filtering. The calcium chloride process thus developed into a calcium dithionate process. Since the latter eliminated the need for make-up calcium chloride, and the dithionate solutions appeared much less corrosive than the chloride solutions, work on the calcium chloride process was dropped in favor of the calcium dithionate process. Acknowledgments The dithionate process was developed by the Bureau of Mines as part of a

Jan 1, 1949

By T. Koulomzine

The theory of the Askania mag-netometer, as well as a complete discussion of all factors influencing magnetometer readings, is very ably described by J. Wallace Joyce.1 We will assume that the reader is thoroughly familiar with this theory and we will use whenever possible the same notations for the physical values involved in the theory. On the other hand, we believe that the principal formulas of the magnetometer can be deduced much more easily by the use of differential calculus than by the methods employed by Joyce. Consequently, we are presenting herewith a resumé of the theory of the vertical magnetometer in order to determine the correct formula of the temperature coefficient which we propose to compensate. Short Theory of the Vertical Magnetometers We shall accept the following notations: m = total mass of the magnet system, in grams. g = acceleration of gravity, in dynes. a = projection on the axis of the magnet system of the distance between the axis of support and the center of gravity of the magnet system, in centimeters. h = projection on the perpendicular to the axis of the magnet system of the distance between the axis of support and the center of gravity of the magnet system, in centimeters. M = 2pL = M, magnetic moment of the magnet system. Z = vertical component of the earth&apos;s magnetic field. ? = deflection angle of the magnet system. = focal length of objective lens in the optical system S = scale reading. In a vertical magnetometer the axis of the magnet system is kept horizontal within 2". Therefore, referring to Fig 1, we see that the magnetic torque of the magnet system influenced by Z must be counterbalanced by the gravity torque. MZ cos ? = mga cos ? + mgh sin ? or dividing by cos ? MZ = mga + mgh tan ? If we now move to another magnetic station and the temperature conditions change, the values of all the variables will change also: M, a, and h under the influence of temperature. 2, both with time and space. ? and S, as a result of all the above changes. Taking increments in Eq 2 we obtain: (Mo + ?M)(Z + ?Z) = mgao + mg?a + mg(h + ?h) tan (? +??) but tan (? +??), because ? is small, can be replaced by tan ? + tan ??; in fact tan (?+ ??) = sin ?.cos ?? + cos ?.sin ??/ cos ?.cos ?? — sin ?sin ?? but sin ? sin ???0 tan (8 + ??) ? tan ? + tan ??. Fur-thermore, neglecting all terms of the equation containing two differentials becomes: or a differential and a tan ??, Eq 3

Jan 1, 1950

By A. J. Opinsky, J. L. Orehotsky, L. L. Seigle

TUNGSTEN incandescent lamp filaments possess a typical structure of elongated crystals generated upon heating the silica-alumina doped wire rapidly to 2200°C or above.&apos; It is known that these very long grains exhibit a preferred orientation, but there is disagreement in the literature about the direction. Rosi,2 and later Rieck; reported that the <135> direction of the large grains in doped wire tends to be parallel to the wire axis, but other investigators have reported that <110> is the preferred direction. Some further investigation of the orientations of large grains in tungsten wire is reported in the following. In the first series of experiments, 6-in. lengths of wire were heated rapidly in a bell jar. Current was passed through the wires and within 15 sec the wires had reached the grain coarsening temperature. 2 min was the annealing time. Wires were heated in hydrogen, nitrogen, and vacuum. Later, wires were heated in an evacuated tube furnace in which the tube was brought from 1000°C to the operating temperature within 25 sec and held 5 min at temperature. Temperatures were measured with an optical pyrometer. After heating, the wires were electro polished and etched, and the orientations of the large grains determined by the Laue back-reflection technique. Most of the experiments were carried out on a single spool of 5-mil silica-alumina doped wire, but a few tests were made with 5-mil thoriated tungsten wire and 10-mil undoped wire. 5-mil silica-alumina doped wires were reduced to smaller diameters by electropolishing for one series of experiments. Orientations of the large grains in silica-alumina doped wire heated in various atmospheres are presented in Figs. 1 and 2 as plots of the direction of the wire axis relative to the cube axes of the crystals. For most of the conditions studied, the preferred orientation cannot be described as a single direction, but the points might be said to group themselves about the arc passing through <110> and <113>. This arc is the trace of the (211) planes and contains the <135> and <124 as well as <011> directions previously observed by other investigators. The preferred orientation of large crystals in silica-alumina doped tungsten wire might be most generally described, therefore, by stating that a (211 ) tends to be parallel to the wire axis. This is true also for wires reduced in diameter by etching and furnace heated, Fig. 2, i.e., the recrystallization texture is apparently unchanged upon removal of the outer layers and substantially independent of the temperature gradient within the wire.

Jan 1, 1962

By W. H. Ashby, R. W. Cassingham, C. R. Blomberg, J. B. Justins

The Brookhaven field is one of several Basal Tuscaloosa reservoirs located in south-central Mississippi. It is a standstone reservoir, of erratic deposition and with several faults, having an approximate subsea depth of 9,800 ft. A large variation in permeability exists with a weighted average being 256 md. Estimated average interstitial water saturation is 45 per cent. The undersaturated reservoir fluid exhibits marked differences in physical properties with measured saturation pressures ranging from 733 to 2,255 psi. Early rapid decline in reservoir pressure caused the operating interests to unitize the field and initiate a program of pressure maintenance by gas injection. At the time gas injection was commenced, the reservoir pressure had fallen to nearly half of the original pressure with only 4.5 Per cent of the original oil in place produced. The reservoir pressure has since been maintained at approximately 2,750 psig, and cumulative production to date is 17 per cent of original oil in place. An analysis of field performance during gas injection is presented in detail. The program of pressure maintenance by gas injection is considered to be a success, since the expected ultimate recovery has been increased and the current production rate is in excess of 2 per cent of original oil in place per year. Performance has been better, anticipated ultimate recovery is larger, and total production costs are lower than for a similar Basal Tuscaloosa reservoir nearby, even though that field appears to have a more effective natural water drive. INTRODUCTION The history of the Brookhaven Unit is a testimonial for unitization and for the application of engineering techniques in the operation of an oil field. The operating and royalty interests in this field have mutually benefited from their early recognition of the need for unitization and pressure maintenance and from the forthright manner in which these were accomplished. The tangible benefits accruing to the participants in the Unit are: (1) income from gasoline plant products, (2) reduced lifting and operating costs from those of competitive operation, (3) maintenance of high levels of current income by mitigation of the inevitable decline in production rates inherent to natural depletion, (4) an increase in ultimate recovery of about 40 per cent over natural depletion operations. This paper should properly be considered a progress report; however, the performance of the field after five years of pressure maintenance clearly indicates that the ultimate success of the project is assured. LOCATION AND GEOLOGY The Brookhaven field is located in south-central Mississippi, about six miles from the town of Brookhaven. Production at Brookhaven

Jan 1, 1955

By S. Yukawa, M. J. Sinnott

A high resolution autoradiographic study of the diffusion of a nickel isotope (NP3) into copper in the temperature range of 650° to 925°C, with particular emphasis on grain boundary diffusion, has been made. The extent of grain boundary diffusion is a function of the grain boundary angle and the diffusion temperature. The ratios of the grain boundary diffusion coefficient to the lattice diffusion coefficient ranges from 104 to 105. The activation energy for grain boundary diffusion decreases with increasing grain boundary angle. STUDIES and reviews&apos;-8 of metallic diffusion have indicated that grain boundary diffusion is a common phenomenon but quantitative studies of the many variables involved are not numerous. The present work was concerned with determining the influence of the crystallographic orientation of the grain boundaries and the temperature on the extent of boundary diffusion of nickel into copper. The study involved essentially three steps: 1—the production of grain boundaries of known crystallographic orientation, 2—the determination of the extent of diffusion into the boundaries, and 3—the analysis of the resulting data in terms of the usual diffusion concepts. The grain boundaries investigated approximated the simple tilt variety having l° of freedom. They were produced by controlling the solidification from a melt of Cuprovac (a high purity vacuum-melted copper obtained from Vacuum Metals Corp.) of a pair of seed crystals so that the bicrystals of copper produced had a common <100> axis. By rotating one seed crystal relative to the other, a simple tilt boundary was produced. The angle of rotation between the two crystals is the grain boundary angle 8, or what is sometimes termed the misfit angle. In all, some 16 boundaries ranging from 2" to 72" in 5" to 10" steps were investigated. The crystallographic orientations were measured with the use of both X-ray and optical goniometric techniques. The <100> axes in the crystals were found to be parallel within 2" to 3" with the exception of one crystal (8 = 12") in which the axes were 6" from being parallel. All bicrystals showed evidences of sub-grain structures. Laue analyses showed that these subgrains differed in orientation up to a maximum of 2". Because of these variations, and some curvature in the boundaries, the grain boundary angles listed are actually average values and deviate from the 1 o of freedom boundaries. The stripping film technique of high resolution autoradiography was used to detect the diffusion of the nickel isotope into the grain boundaries of the bicrystals of copper. Kodak experimental permeable stripping film with an emulsion layer 5 u thick

Jan 1, 1956

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

IT was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a. component of the pulp, of a mass solubility of the general order of a fraction of a milligram to 15 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.2 The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. EXPERIMENTAL Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well beyond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipita-

Jan 1, 1943

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts&apos;2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By V. F. Leferrer

A new process for the treatment of silver crusts from desilverization of lead has been developed by Societe de Penarroya. The zinc contained in the crusts is recuperated by vacuum distillation at low temperature. The use of special retort crucibles is avoided. AT Noyelles-Godault the Parkes process (zinc addition to a silver-bearing lead melt) is used to desilverize lead bullion from the blast furnace. The crust which rises to the surface of the bath is removed and pressed by a well-known process in a press of the Howard type. The pressed crust, called zinc crust or silver crust, contains 10 pct Ag, 30 pct Zn, and 60 pct Pb. It is melted under a salt bed in a small, narrow, and deep kettle heated only in its upper part. A liquid concentrated alloy is obtained which is called T.A.C. in France (triple alliage concentr6) analyzing approximately 25 pct Ag, 65 pct Zn, 8 to 10 pct Pb, and 1 to 1.5 pct Cu. This T.A.C. is a real metallic alloy, completely deoxidized, and can be stored indefinitely. The process used at Noyelles-Godault consists in distilling this alloy in a tight furnace, under low vacuum and at low temperature, so that only the zinc distills and is condensed into liquid form. The residual silver-bearing lead is almost entirely free from zinc and oxidized dross. The vacuum dezincing equipment, see Figs. 1 and 2, consists of: 1) A furnace, constituted of a casing of steel plate lined with refractory bricks, heated internally by means of graphite resistors. The temperature of the furnace is measured by a thermocouple device and controlled by an automatic temperature regulator which acts upon the flow of the current passing through the resistors. Two doors, numbered 1 and 2 in Fig. 2, are provided for, one for charging the T.A.C., the other for tapping the high silver-bearing lead. 2) A condenser, and an ordinary room lined with good heat conductor refractory material. This condenser is provided with a graphite resistor which serves to bring to temperature when starting the furnace. A thermocouple records the temperature of the zinc melt and controls the temperature in the furnace, that is, the flow of current through the resistors, by means of the above mentioned regulator, so that the distillation rate in the furnace does not exceed that of the condensation. The condenser is connected to the vacuum pump by a filter. The whole equipment should, of course, be fluid-tight. The operation is carried out under a vacuum of about 10 mm Hg.

Jan 1, 1958

By R. Bakish, W. D. Robertson

IN the course of a study of stress corrosion cracking of AuCu,, it was necessary to develop new electropolishing and metallographic etching methods. The techniques are generally useful for Cu-Au alloys, including the AuCu composition in which transformation markings are well delineated. For electropolishing, the only satisfactory electrolyte and procedure that has been found1 has the composition given in Table I. The solution must be vigorously stirred while polishing and the temperature maintained in the range of 55" to 62°C. The electrolyte is very unstable and can be used only for 10 to 15 min after which its color changes and a dark-brown precipitate forms. The polishing time is between 1 and 4 min depending on the initial surface preparation. The use of a hood is recommended to avoid the danger of cyanide gas which may form at one of the electrodes even though the solution is alkaline. The optimum current and voltage conditions for vertical anode and platinum cathode are on the plateau shown in Fig. 1, in which voltage is measured across the cell terminals. At voltages below the plateau, etching of grain boundaries occurs and under some conditions, which have not been clearly defined, octahedral etch figures are observed. For general purpose grain-size determination in polycrystalline alloys, a 3 pct solution of iodine in methyl alcohol is used with excellent results. However, when it is necessary to reveal small orientation differences or concentration gradients in an alloy, the iodine etch is not satisfactory. For this purpose, a highly satisfactory etching procedure was developed during this investigation. It involves the use of the vapor given off by freshly prepared aqua regia. The solution employed is 3HC1 to lHNO, which decomposes in accordance with the reaction HNO, + 3HC1 = NOCl + 2H,O + Cl,. The polished specimen surface is held about 1 to 2 cm above an aqua regia solution for 2 to 10 sec depending on the intensity of the contrast required and the surface is not subsequently washed. The results obtained with a coarse grained cast structure are shown in Fig. 2. Subgrain boundaries in a single crystal and concentration gradients within the boundaries are developed by the same treatment with the results shown in Fig. 3. Obviously, any conclusions regarding structure-dependent properties will be modified by the pronounced heterogeneity, which is not clearly evident when more conventional methods are used. Interesting structural details are also revealed by treatment for 4 hr at 850°C in unpurified tank argon. Fig. 4 shows a pattern characteristic of orientation-dependent oxidation.

Jan 1, 1956

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.&apos; Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy&apos;s law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f&apos;(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f&apos;(S) can be calculated. It turns out that the experimentally derived f&apos;(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-