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By T. D. Tiemann

The purpose of this writing is to make available additional data, not previously published, on the extraction of silica from certain iron ores of Wisconsin and Minnesota and to discuss a possible method of processing. Results of investigations on the extraction of silica from low grade iron ores have been previously presented and discussed in detail in AIME Transactions.1,2 All of the ores investigated are essentially nonmagnetic and consist mainly of hematite, goethite and quartz. Much of the quartz is microcrystalline, particularly in the taconites. The ore from the Cuyuna range contains in addition manganese oxides. Briefly, the method consists in digesting a sample of the ore under pressure in a solution of sodium hy-

Jan 1, 1965

By Harry H. Power

The relative merits of air and natural gas as propulsive agents in pressure drive operations have been discussed for a number of years. When air or gas is introduced into the sand, various factors lead the operator to the selection of what he believes to be the proper propelling medium; but when the question of relative drive effect is raised, several physical and chemical premises must be taken into consideration in arriving at a conclusion as to the superiority of one medium over the other. Dow and Calkins1 and Beecher and Parkhurst2 have contributed fundamental experimental work on the effect of dissolved gas in lowering the viscosity and surface tension of crude oil. Herold; and Tickell' have indicated that whatever type of reservoir control obtains, gas plays other important parts in the movement of oil towards the well, namely: 1. The propulsive and expansive force of the gas. 2. The "Jamin effect," or resistance to the movement of oil in a porous media due to the formation of gas bubbles. When quantitative studies are made, parallel conditions must be selected whereby we may say definitely whether air is superior to gas as a driving medium, or vice versa. Examples of similar conditions are not easy to find in the field. However, in the laboratory we can make determinations which may lead to general conclusions when applied to the field. The experimental and research work described here was started at the laboratories of the University of California in January, 1927, and completed in private laboratories at Tulsa, Okla., in February, 1928. The apparatus used was designed especially for the work.

Jan 1, 1929

By G. W. Thomas

A mathematical tnodel of forward combustion in an oil reservoir is treated in this paper. The model describes a radial system having a vertical section of essentially infinite thickness, all of which is permeable to gas flow. Combustion, however, is presumed initiated over a limited thickness of the total vertical section. In the interval supporting cotnbustion, the mechanisms of radial conduction, convection and heat generation are taken into account. Above and below the burning interval, heat transport in the radial direction is by cottduction and convection. Vertical heat losses from the ignited interval are accounted for by conduction alone. A general solution is presented for the temperature distribution caused by radial movement of the combustion front. The results show that no feedback of heat occurs into the ignited interval when convection and conduction are acting in the bounding media. Peak temperatures are also 5 to 10 per cent higher than in the case where heat transport in the bounding media is by conduction alone. We arbitrarily define vertical coverage to be that fraction of the total ignited interval which is at 600F above atnbient, or greater, at any given time. The radial distance at which the vertical coverage becomes zero is the propagation range of the combustion front. It was found that an increase in vertical coverage results when the oxygen concentration, fuel concentration or gas-injection rate is increased. Moreover, the combustion front can be propagated 10 to 15 per cent further than in the case where only conduction is acting above and below the ignited interval. INTRODUCTION In the theoretical treatment of forward combustion in a radial system, one of the problems encountered is the determination of the transient temperature distributions caused by an expanding cylindrical heat source. Bailey and Larkin' and Ramey' simultaneously presented analytical solutions to the problem assuming heat transport by conduction alone. In a subsequent publication, Bailey and Larkin3 included the effects of both conduction and convection while treating linear and radial models. In this latter work, however, vertical heat losses were largely neglected. Selig and Couch' dealt with a radial model in which both conduction and convection were acting. Only a limiting case involving vertical heat losses was considered, however. Namely, temperatures on the boundary of the bed of interest were set equal to zero. Solutions thus obtained were representative of a system having a maximum vertical heat flux. Chu5 recently treated a more general case in which a permeable bed was considered bounded by impermeable media. Conduction and convection took place within the bed, and only conduction outside of the bed. The effects of vertical heat losses were included in his study. Solutions were obtained by numerical techniques. This paper is an extension of the theoretical work of other authors pertaining to forward combustion in a radial system. In particular, a mathematical model of the process is treated in which heat generation occurs over a small vertical interval of a larger permeable section. In the interval supporting heat generation, and above and below this interval, the mechanisms of radial conduction and convection are also presumed acting. Heat losses from the ignited interval are accounted for by vertical conduction. An analytical solution for the temperature distribution caused by radial movement of the burning front is presented. The effects of certain process variables are indicated and comparisons with Chu's results are made. THEORY To render the mechanism of forward combustion tractable to mathematical treatment, we idealize the problem to the extent of assuming continuous reservoir media possessing homogeneous and isotropic properties. The following additional assumptions are implicit in this analysis. 1. The thermal parameters, i.e., heat capacities, thermal conductivities and thermal diffusivities are invariant with temperature and pressure. Moreover, the bounding media possess the same thermal properties as the bed of interest. 2. The temperatures of the porous media and its contained fluids at any point and at any time are equal. 3. The reaction rate between the oxidant gas and the fuel is infinite. This assumption implies that the incoming oxygen concentration instantaneously goes to zero within an infinitesimal distance, i.e., the width of the combustion zone is negligible. 4. The rate of gas injection is constant and corresponds to the average rate throughout the lifetime of the project. 5. The fuel concentration is constant throughout the volume of rock swept out by the burning zone. 6. There is complete burnoff of fuel. This assumption demands that the rate of propagation of the burning front equals the rate of fuel burnoff. In a radial system, with a

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.' The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

Discussion of the paper of GEORGE S. RICE and H. H. CLARK, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2563 to 2571. NORMAN V. BRETH,* Pittsburgh, Pa.-It was my privilege to visit in the last two months on behalf of the U. S. Bureau of Mines 10 mines where electric shot-firing systems controlled from outside the mine are installed. I will describe briefly what I saw in some of these mines, which are located in Utah, New. Mexico, Oklahoma, Alabama, and Kansas. At a mine in Utah, 230-volt alternating current is used to fire the shots, which is taken from a small transformer in the substation. The shot-iring circuit is independent of all other wires and is tested for grounds every day. There are no lightning arresters on the firing circuit. Porcelain insulators are used inside of the mine, and glass outside. The switches are situated as follows: One in the substation, one in, the shot-firer's cabin, two at each cross entry; where the shot-firing circuit crosses the trolley wire a switch is placed on either side of the entry in series with the shot-firing circuit. The miners are checked in and out of the mine. The coal is undercut and is shot down with permissible explosive, the shots being connected in multiple. There are 75 to 110 shots fired each day. A great many times there are no missed shots. If not more than two or three are missed they are left until next day. The fan is kept running at full speed when the shots are fired. The shot-firing switch is closed only once and the whole mine is shot at once. At another mine in Utah, power wires are used for shot-firing circuits; 500-volt, direct current is used to fire the shots. The only sizes of wire used outside of the power wires are Nos. 8 and 14 B. & S. gauge. The return is connected to the pipe lines and track. Porcelain insulators are. used inside of the mine.

Jan 4, 1915

By S. F. Shaw

The principles involved in lifting oil in wells flowing naturally are identical with those underlying the flowing of wells by means of the air-gas lift, and information of a dependable nature obtained in the study of the air-lift can be applied to wells with natural flow. A well flowing naturally is one in which the lifting is done by means of the gas-lift, for which the gas is supplied entirely by the formation from which the oil is derived. In air-gas lift operations, there is insufficient gas supplied by the formation to lift the oil to the surface in an efficient manner, therefore additional gas for this purpose must be furnished from an outside source. There may, at times, be conditions obtaining in natural flowing wells different from those in wells flowed by gas-lift, but these differences do not at all conflict with the main principles of gas-lift work. One such condition is met with in wells in which the gas supplied by the formation is in considerable excess of that required to lift the oil to surface; this excess may be so great as to reduce the quantity of oil that can be lifted through the particular diameter of casing or tubing that has been lowered into the well. This same condition can be brought about, however, by supplying a large excess of gas from an outside source to an artificial gas-lift well, and a study of the effects obtained from injecting a large excess into the well can be applied directly to handling wells flowing naturally which have a large excess of gas supplied by the underground reservoir. Conditions for Lifting Oil The main factors to be considered in flowing wells are as follows: 1. Submergence, or pressure at the bottom of the tubing or casing. 2. Lift; the height to which the liquid must be raised. 3. Diameter of the flow tubing or casing. 4. Quantity of liquid to be lifted. 5. Pressure at the discharge end of the flow tubing, or back-pressure, as it is sometimes called.

Jan 1, 1930

By D. J. Schmatz

DISCUSSION OF RESULTS The qualitative correlation between low-temperature ductility and prior high-temperature creep strain in nickel obtained in this investigation confirms the result obtained on high-purity brass by Chen and Machlin. However, the quantitative effect is much smaller in nickel. Comparison can be made on the basis of a prior high-temperature strain that is a certain percentage of the total high-temperature elongation to rupture. In the research of Chen and machlin, the prior high-temperature strain of 1/2 pct equaled 8.5 pct of the total high-temperature elongation at rupture. For nickel, in our experiments, 8.5 pct of 21.2 pct equals 1.8 pct. For eh = 1.8 pct, the loss in ductility in percent equals x 100 = b.5 pct. That is, for equivalent bo Formation of Beta Manganese-Type Structure in Iron-Aluminum-Manganese Alloys D. J. Schmatz IRON-aluminum alloys have gained much interest in the past few years for use as a base material for elevated-temperature alloys because of their excel- high-temperature strain the loss in low-temperature ductility is 8.5 pct for nickel as compared to 60 pct for pure a, brass. It is also interesting to note the observation that in nickel the low-temperature fractures, even at the most extreme high-temperature pre-strain, were partly trans crystalline and partly intercrystalline. In the case of a brass, these fractures were completely intercrystalline. According to the data on the percent of the grain boundary area that is cracked, at 22 pct high-temperature elongation, about 12.5 pct of the grain boundary area does not carry load. Thus, the inter-crack areas are carrying a stress that is about 11 pct higher than the nominal stress. A simple model predicts that the overall elongation, which is primarily the elongation in the bulk of the specimen, will correspond to the nominal stress when the stress in the intercrack area equals the tensile strength. Quantitatively this model predicts the equation The form of this equation will agree with that found if the strain-hardening exponent, n, equals unity. Actually this model is too gross an approximation to yield good quantitative results. The question naturally arises as to whether in ordinary hot-working, such as hot-rolling, intercrys-talline cracks are introduced that affect the low-temperature properties. It appears that the answer is that such a possibility cannot be overlooked, if the hot-working induces tensile stresses at temperatures above the equicohesive temperature and if the material tends to be notch sensitive at low temperature. ACKNOWLEDGMENT This research was supported by the Aeronautical Research Laboratory, Directorate of Research, Wright Air Development Center, United States Air Force. REFERENCES lC. Zener: Fracturing of Metals, 1948, Cleveland, ASM. 'H. C. Chang and N. J. Grant: Mechanism of Intercrystalline Fracture. AIME Trans., 1956, voL 8, p. 544; lownal of Metals, May, 1956. 'E. S. Machlin. CreepRupt ure by Vacancy Condensation, AIME Trans., 1956, vol. 8, p. 106; lownd of Metals, February, 1956 'C. Chen and E. S. Machlin: On a Mechanism of High-Temper at ure Inter-crystalline Cracking, lownd of Metals, July. 1957. p. 829. Alloys lent oxidation resistance. Binary alloys of aluminum in iron are ferritic and consequently have poor hot strength. Alloys of iron-aluminum-manganese were made in an attempt to produce an austenitic alloy containing sufficient aluminum to retain the oxidation resistance of binary alloys of iron-alumi-

Jan 1, 1960

By Joseph Jensen

California's outstanding contribution to unit operation is the plan of development now established for the North dome of the Kettleman Hills. Beginning April 1, 1931, the Kettleman North Dome Assn. will control the unified operation and development of 10,800 acres of proven and semiproven oil land, and at the same time the Standard Oil CO. of California will operate as another unit its fee land of 9460 acres of similar character. The holdings of the two companies are in a checkerboard mile-square pattern. In addition to this, 410 acres of land may yet be included in the Kettleman North Dome Assn. unit and 530 acres of land are definitely out of both units. The owners of some of this land have expressed their intention of cooperating in a reasonable way with these two units. Cooperative agreements are now in force as to most of this field. Under the definitions of a unit pool and a near-unit pool,' the operation at Kettleman Hills will be a near-unit operation, but because of the size of the structure and its proven highly productive character, the arrangement. concluded on Jan. 31, 1931, in the approval of the Kettleman North Dome Assn. Agreement by Secretary of the Interior Ray Lyman Wilbur and by California State Oil and Gas Supervisor R. D. Bush is of outstanding importance to the entire oil industry. No other major unit operation plans are under way in California at the present time. There has been some little discussion of a plan in the North Belridge field and a feeling that the discovery of oil in the Lost Hills field and also in the South Belridge field would necessitate consideration of unit plans. So few data are available for these areas, as to the land that should be included in such unit plans, that little constructive action is now possible. The beginning of drilling on the Middle dome of the Kettleman Hills also makes it an area deserving consideration for unit operation. All four of the above-named areas lie on the west side of the San Joaquin Valley, in Kings and Kern counties, to the south of the

Jan 1, 1931

By L. Russell, van Wert

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By van Wert, L. Russell

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By Henry M. Howe

in Cast-Iron. It has been generally accepted that the presence of silicon in cast-iron leads to the formation of graphite; and this has been explained by saying that the silicon lowers the solvent power of iron for carbon at and somewhat below the freezing-point, so that, in the presence of silicon, the iron is unable to retain in solution or combination the whole of the carbon with which it has united while molten, and therefore expels the excess of carbon in the form of graphite, during and immediately after solidification. Probably the best way to study this question would be to examine pure cast-irons, i.e., those containing nothing but iron, carbon and silicon, which at the same time should have been saturated with carbon when molten. But the data for such a study are not at hand; so we must turn to commercial pig-irons as they are made in the blast-furnace, and before their composition has been changed by remelting. Much evidence has been offered of late, tending to oppose the theory of the action of silicon above set forth. Some of this evidence will be examined here. 1. Mr. Bachman's Results. In particular, Mr. F. E. Bachman† has published a collection of analyses of cast-iron, in which the proportion of graphite at first appears to be nearly independent of the proportion of silicon present. Thus, in his Table LI., we find that with pro-

Jan 1, 1901

By R. S. Hadi, L. Svarovsky

SUMMARY This is a report of a new development in on-line particle size measurement of fine powders in dust-laden gases. A continuous sample of the solids-air suspension is drawn from the process stream via a sampling probe by means of an air operated ejector into a cyclonic separator whereby the sample is subjected to a particle size dependent separation process and split into two streams, "overflow" and "underflow". The overflow stream carries most of the fines at a relatively low concentration and the underflow stream carries the coarse particles at a relatively higher concentration. The concentration of solids in the two streams is detected by electrostatic noise level technique which utilises the electrostatic charge accumulated on the solid particles due to their high velocity in the turbulent air stream, for the mass concentration measurement. The ratio of the solids concentration of the fines stream to that of the coarse stream is then correlated against the average particle size in the main process stream by a calibration curve. The in-plant tests clearly indicate that this relatively simple instrument offers good sensitivity in the size range from 2 to 6 µm, and is capable of giving a continuous indication of average particle size for process control purposes. Although the instrument was developed for a particular application, it may be used in other situations where fine powders are conveyed in gas streams. British and foreign patents are applied for.

Jan 1, 1980

By Lawrence B. Wright

The occurrence of gold, gold-silver, silver-lead-zinc ores in the post-Cambrian sediments in the Black Hills of South Dakota, and their genetic relationship to the Tertiary intrusives, is well known and accepted, but the occurrence of gold in the pre-Cambrian rocks at the Homestake mine, which underlie this Tertiary gold mineralization, has given rise to differences of opinion as to the period of major gold introduction into the older rocks. Fig. 1 illustrates the distribution of mineralization along the axis of the Tertiary uplift in both pre-Cambrian and post-Cambrian rocks. The following possibilities have been presented: 1. The Homestake gold deposit was formed in pre-Cambrian time and the deposits in the overlying Cambrian sediments formed during Tertiary time. 2. The Homestake lode existed at the beginning of Cambrian time, but was enriched by the passage of Tertiary auriferous solutions. 3. The Homestake lode was represented by pre-Cambrian quartz-chlorite sulfide mineralization, very low in gold content and the gold superimposed on the older nearly barren mineralization during the Tertiary metallogenic epoch. 4. The sulfides and sulfarsenides as well as gold were deposited in both pre-Cambrian and post-Cambrian rocks during the Tertiary period. Those favoring the first proposition feel that the question is pretty well settled, while the proponents of the second theory are more flexible in their view, feeling that the amount of gold introduced in either period is still an open question. The third and fourth theories, with some modifications, are supported by the proponents of the Tertiary theory, who feel that the evidence strongly favors that period. The following pages are intended to present the evidence and to give the reaction of various observers with my own comments and conclusions; also, the accumulated facts of observation gathered over a period of close association with the area under discussion, beginning in 1919.

Jan 1, 1937

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By David L. Holt, Walter A. Backofen, Anwar-uI Karim

Specimens of a hydrided Mg-0.5 Zr alloy were strained in tension at 500°C and constant rates of 2 x10-3 5 x 10-3, and 2 X 10" min-1. Hydride-denuded zones formed at grain boundaries normal to the tensile-stress direction as a result of magnesium transport during difusional flow. The width of the zones could be measured and the measurement used for calculating the diffusional component of the imposed tensile strain. The strain from diffusional flow was found to increase with imposed strain at a diminishing rate, tending to saturate at approximately 12 pct. Strain rate sensitivity of flow stress was low. The apparent non Newtonian character of the diffusional flow is attributed to a non Newtonian process acting in parallel with it which could be boundary shear. Fracture grows out of voids that form in the denuded zones. DEFORMATION of a grain by diffusion of atoms from boundaries stressed in compression to boundaries stressed in tension is Newtonian viscous,1-3 and evidence has accumulated in recent years that such a process may be responsible for the high strain-rate sensitivity of the flow stress of super-plastic alloys.4"7 One piece of evidence is that experimental stress: strain-rate relationships can be quantitatively explained.5-7 There is also metallo-graphic evidence of diffusional flow in superplas-ticity, but in a limited amount. The formation of striated bands on the surface of superplastically deformed specimens has been attributed to diffusional flow.5"7 The basis of that attribution came from experiments on a coarse-grained, nonsuperplastic and hydrided Mg-½ wt pct Zr alloy which formed hydride-denuded, light etching zones at tension-stressed boundaries when strained in tension at 270?C.6 The origin of these zones had already been traced to the diffusional flow of magnesium atoms to the boundaries.' The particular observations in the more recent work were of striated-band formation on the surface and denuded-zone formation internally, with both the bands and zones having the same width and appearing at tension-stressed boundaries. It was argued that the bands were a surface manifestation of the zones and hence of diffusional flow. Of course in superplastic alloys which do not contain internal metallographic "markers", the surface bands can be the only metallographic indication. In the present work, denuded-zone formation was utilized, as it has been by others,9-11 to extend the observations of diffusional flow and to measure the strain, ed, resulting from it. Grain size had to be large to measure ed with accuracy. The grain size chosen for this study was -30 , and with that a strain of 10 pct from diffusional flow produces a denuded zone only 3 µ in width. The large grain size naturally precludes superplasticity. The observations of diffusional flow were complemented by determining the strain from the other operative deformation modes: slip, e,, and grain boundary shear, egb. An incremental specimen extension is the sum of increments from slip, and grain boundary shear as well as diffusional flow. Division by a common length is required to convert to strain. If this length is taken as the initial specimen length, then imposed engineering strain, e, is given in terms of the component engineering strains by e = ed + es + egb [1] Stress:strain-rate relationships are determined by the way in which this "strain balance" is made up. EXPERIMENTAL Material. Zirconium hydride markers were introduced into the Mg-0.5Zr alloy by annealing in hydrogen at 450°C for 30 min. The hydride concentration was particularly high at zirconium rich stringers, which was fortunate in that the transverse boundaries at which denuded zones form lie perpendicular to the stringers. Grain size after annealing was 30 µ. Photomicrographs of unstrained and strained material are shown in Fig. 1. Procedure. Specimens were strained in tension with an Instron machine at crosshead velocities of either 2 x 10"3, 5 x X or 1 x 10-2 in. min-'. Specimen length and diameter were 1.0 and 0.2 in., respectively, so that initial strain rates in tests at constant crosshead speed were 2 x 10"3, 5 x X and 1 X l0-2 min-1. Tests were made at 500°C which is a compromise temperature at which diffusional flow is still measurable but grain growth is not active enough to interfere with metallographic measurements. The tests were made in a hydrogen atmosphere. Strain Balance. An equation additional to [I] is eg = ed + es [2] where eg is strain measured from grain elongation. Measurement was made of ed, eg, and, of course, e, which enabled all the strains in Eq. [I] to be determined. For this purpose, strained specimens were sectioned longitudinally, polished, and etched. The strain from diffusional flow, ed, was computed by measuring on photomicrographs the width in the tensile direction of denuded zones at either end of a grain XI, X2, adding them, and dividing by twice the initial longitudinal grain dimension L0, Fig. 2. Reported values are the results of measurements on seventy randomly selected grains; 95 pct confidence limits on ed were +1.5 pct strain. To measure eg, the maximum length, L, and the maximum width, W,

Jan 1, 1970

By R. H. Goodrich

Development in this district during the year 1929 was little different from that of any other year despite the somewhat depressed condition of the oil business in general. The year was marked by: (1) An intensive geophysical campaign in the search of deep-seated salt domes; (2) the rather successful exploration and development of lateral sand production on the flanks of some of the older domes. Geophysical Exploration Geophysical work is confined almost exclusively to the torsion balance and seismograph. At the beginning of the year there were approximately 185 individual instruments of all types engaged in the search of structures in the Gulf Coast of Texas and Louisiana. This total includes 3 magnetometers, 83 torsion balances and 100 seismographs. The number of parties operating the torsion balances was 47; seismographs, 20; magnetometers, 3. It is estimated that 4,800,000 lb. of dynamite or other explosives were used in seismic exploration. During the year the torsion balance and seismograph were credited with having discovered the following salt domes: Texas, Danbury dome, Brazoria County, H. & T. B. R. Co., and Clodine dome, Fort Bend County, John Fredricks and Wm. Stanley, Satowsky Survey; Louisiana, Iowa dome, Calcasieu and Jefferson Davis Parishes, T. 9 S., R. 6 and 7 W., and Cameron-Meadow dome, Cameron Parish, T. 14 S., R. 13 W. Because of the secrecy maintained in these developments, it is somewhat hazardous to venture opinion as to the number of salt domes found during one year. The discovery of gas at Mykawa district and at Genoa district, in Harris County, Texas, is considered of more than passing importance, because there is indication in the performance of these two districts that commercial accumulation of oil and gas may be found in the Gulf Coast on structures other than the wore or less definite salt dome type. While it is generally conceded that the accompanying structure in these instances are deeply buried salt domes, it is a fact that neither the seismograph nor the drill have indicated the presence of salt.

Jan 1, 1930

By M. B. Kasen

eralized strain equation appear quite different they are really identical. This identity can be shown in a simple mathematical rearrangement. Referring to Eq. [I], the substitution of ln(1 +?E) for ? (where ?E is the engineering strain) yields: a =s8- (s8?so)e?1/?c) ln(1 +s8??E) [4] or s =s8?(s8?so)(l +?E)-1 [5] Replacing (1 + cE) with its equivalent, (l/lo): s=s8?(s8?so)l/€c [6] Adding and subtracting the quantity (s8 - so) yields: s=s8?(s8?so)+ (s8-so) l-(^)l/£c [7] = s0+(s8?so)ri-(^0)1/^l [8] Letting n = 1/?c it follows that: This equation will be seen to be identical to the generalized strain expression in Eq. [3], the coefficients a and b being equal to so and (s8?so)/?c or n(s8?so), respectively. Confirmation of the relationship noted above was provided by fitting experimental stress-strain data5 for 304 stainless steel (total strain from 0.072 to 1.15) at room temperature at a true total strain rate of 4 x 10-3 sec-1 to Eqs. [I] and [3]. In this study nonlinear regression analyses were used to evaluate the equation constants. The results of this evaluation are presented in Table I. When these constants are used in Eqs. [I] and [3] the curves obtained are coincident. It will also be noted that the value of n is equal to YE,, the value of a is equal to so, and the value of b is equal to (s8 - so)/Ec. These equalities are illustrated in Table I where the Voce constants in parentheses were calculated from a, b, and n values. Excellent agreement is seen to exist. It is concluded, therefore, that the Voce equation is, indeed, identical to the linear expression involving generalized strain. In applying the generalized strain concept to stress-strain data, it has been noted3 that data within what was termed the transition region (first few points in the plastic flow region) must be excluded from the analysis in order to obtain the linearity in Eq. [3]. A similar exclusion applies in the use of the Voce equation since an expression which would describe the strain-hardening region would usually be found to be not too effective in the elastic-plastic fillet2 which connects the elastic line to the strain-hardening region. These considerations further substantiate that Eqs. [I] and [3] do indeed describe identical behavior. Note added in proof. Since this manuscript was submitted for publication, correspondence with Professor S. R. Davies, University of Edinburgh, (of Ref. 3) indicated that his associates have also confirmed the identity between the Voce equation and the generalized strain concept. It is sometimes desirable to obtain a small grain size in super-purity metals. Unfortunately, the absence of impurities, the low recrystallization temperatures, and the low activation energies for boundary motion result in rapid growth of relatively few grains when conventional recrystallization practices are used. For example, Arajs et al.1 were unable to obtain a mean grain diameter less than about 0.4 mm in iron containing 38 at. ppm of impurity. The <1 at. ppm purity range in many modern superpurity metals results in yet larger limiting grain sizes. It is the purpose of this communication to describe a technique by which mean grain diameters as small as 30 µ have been produced in aluminum having an impurity content < 0.5 at. ppm. The technique should be applicable to superpurity metals other than aluminum and has potential applications to grain refinement of commercial alloys. The necessary and sufficient requirements for production of a small grain size are as follows: a) a large number of potential nucleating sites must be created randomly within the cold worked material, b) sufficient thermal energy must be provided at a rate that will simultaneously activate a large fraction of the potential nuclei, and c) the grain growth must be stopped shortly after grain impingement.&apos; A high density of potential grain nuclei may be cre-

Jan 1, 1970

By E. O. Jones, E. Whitehead

During the heating of cold-worked nickel silver, the tendcncy of the material to crack is well known. The present research deals with this question, and may conveniently be divided into the following sections: Changes in these alloys during heating and cooling, determination of the temperature at which cracking occurs, effect of grain size, quenching cracks, methods of overcoming annealing cracking. The work is far from complete, in particular the influence of impurities on this tendency has not been investigated, but the results so far obtained lead to certain definite conclusions, which are of theoretical and practical importance. Changes in Alloys During Heating and Cooling During the annealing of many metals at a temperature just below that at which recrystallization sets in, there is evidence of some change, the effect of which is to harden and embrittle the material. This effect has been most clearly demonstrated in the cases of aluminum, copper, brass, and nickel silver, and appears to be a common property of cold-worked metals and alloys, or, at any rate, the non-ferrous ones. The effect would obviously offer an explanation for certain types of annealing cracking, but the trouble is so much more common in the nickel silvers than in the other alloys that some special cause should be looked for. There is, however, fairly good reason for believing that similar cracking may occur in some of the brasses; D. Bunting1 suggests that the a brasses toward the saturation limit are subject to a transformation closely allied in nature to that known to occur in the nickel silvers at around 320" C. Although the existence of this critical temperature range was known, it did not necessarily follow that this transformation was responsible for the trouble under investigation, so the first portion of this paper deals with the attempts made to determine whether other critical changes might not occur in these alloys. There were already reasons for the belief that such would prove to be the case, as the mechanical properties of the nickel

Jan 1, 1926