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By Carleton Ellis

(Presented at a meeting of the New York Local Section of the Institute, Apr. 12, 1912.) I. INTRODUCTION. THE problem of the influence of hot surfaces upon gaseous combustion is one which, from a purely scientific stand-point, has engaged, for many years past, the attention of Prof. William A. Bone, of Leeds University and the Imperial College, London; and as his recent work has been the direct outcome of earlier scientific investigation, it will be appropriate, by way of introduction, to review briefly the present position of science with respect to this important subject, as stated by Professor Bone. One may perhaps best arrive at an understanding of the term " ?flameless " or " surface " combustion by considering certain facts which differentiate it from the more familiar processes of combustion as they occur in ordinary flames. All hot surfaces have an accelerating influence upon chemical changes in gaseous systems. If, at any temperature, a gaseous system, A, tends to pass over into another system, B, contact with a solid at the same temperature will accelerate the process. To take a very simple example, if a mixture of hydrogen and oxygen in their combining proportions (electrolytic gas) were maintained in an inclosure with smooth glass walls at a temperature of, say, 450° C., there would certainly be a tendency to form steam, but the rate of change would be negligibly small. If, however, there were brought into the system some porous solid material at the same temperature, so that a large surface was exposed to the gases, the rate of change would at once be rapidly accelerated in the layer of gas immediately in contact with the hot surface. Steam, the product, would diffuse outward from the surface, and the supplies of hydrogen and oxygen at the surface would be renewed by diffusion inward. Thus combustion would proceed heterogene-

Sep 1, 1912

By H. H. Hausner, H. S. Kalish

M. Hansen—This paper certainly is an interesting study. Although I have not had too much experience in the powder metallurgical methods of studying phase equilibria, I would like to say the following concerning the interpretations of the results obtained: 1. The existence of a zirconium-rich eutectic having a melting point close to 950°C and containing approximately 5 pct beryllium is well established. 2. Undoubtedly sintering of the original compacts (i.e., without repressing and resintering at 1350°C) resulted in a condition being far from equilibrium, even in the low-melting point zircon-rich region where undissolved zirconium particles have been observed. This means that only partial reaction between the component powders has taken place. 3. In preparing and handling powder mixtures for pressing and sintering, we have found that with powders differing considerably in density, and also in particle size, separation in layers of different composition may occur. This means that a concentration gradient would exist within such samples. This phenomenon may, at least to some extent, account for the difference in microstructure of the top and bottom regions of some of the sintered samples. If this is the case, density figures for some of the nominal compositions would not represent actual densities of those mixtures. 4. Fig. 1 shows that the low densities of mixtures with 40 and 60 pct beryllium sintered at 1350°C are changed to much higher densities if the products sintered at 1100°C are repressed and resintered at 1350°C, whereby an approach toward equilibrium takes place. This would mean that the low density and growth in volume is due to nonequilibrium conditions. If this is true, would it be justified, then, to conclude that "the remarkable growth of the alloys in the vicinity of 40 to 60 pct Be indicates the formation of a high-melting point phase, probably accompanied by a considerable change in volume due to a large alteration of the crystal structure from that of the original compounds"? If some compound formation has taken place already during the first sintering at 950" to 1350°C, more compound would be formed by repressing and re-sintering of the 1100" samples. This treatment, however, results in higher, rather than lower, densities. In general, the density-composition curve of alloy systems containing one or more intermediate phases is characterized by a more or less defined contraction (decrease in specific volume, increase in density) over the "theoretical" density. Does not discrepancy exist between the two statements that "growth of the alloy indicates the formation of a high-melting phase . . ." and "even at 1350°C, no indications of sintering have been observed"? 5. I am not sure that the explanation given for the fact that fig. 4 did not reveal as much eutectic as the top portions of the mixture with 2 pct Be, is correct. The density of the melt containing only 5 pct Be or even perhaps less, is not too much different from that of the nominal composition. The reason might be also that there was already some separation of the components in the pressed compact. 6. I do not understand why the microstructure of the bottom regions of the compact with 5 pct Be (fig. 6) is so different from that of the top regions (fig. 5). The compact was melted on sintering at 1100°C. Its composition lies close to the eutectic point. There should be at least some lamellar structure in the bottom regions too; otherwise, the composition of top and bottom must have been very different after sintering, because the eutectic is said to extend as far as the composition ZrBe2. In case the white and gray areas of fig. 6 are both gamma, and the black areas undissolved zirconium, this composition would be close to the phase coexisting with zirconium, that is, ZrBe2, according to the hypothetical diagram, or a compound richer in zirconium. 7. Figs. 9 and 10 are not mentioned in the text. 8. The great difference in microstructure of the composition 20 pct Be of figs. 8 and 14 on one side and fig. 15 on the other side proves that sintering at 950" and 1100°C results only in partial reaction of the powers. 9. The mixture with 60 pct Be (fig. 19) seems to consist of two phases, rather than one phase, one interspersed in a matrix of another. 10. The statement that the eta phase "may be an intermetallic compound or the product of a peritectic or monotectic reaction" seems to be misleading, because the product of a peritectic or monotectic reaction in this region of the system must be an intermetallic compound. 11. If there is some solid solubility of Be in alpha and beta-Zr, it would be expected to be higher in beta-Zr (b.c.c.) than in alpha-Zr (h.c.p.). The temperature of the polymorphic transformation of zirconium then would be lowered, rather than increased. In accordance with this, Battelle has found that the transformation point of titanium is decreased by beryllium. 12. In case the phases present in alloys with 80, 90, and 95 pct Be are identical (which appears to be correct), it is striking that the relative amounts of both phases (eta and beryllium) are not too different within this wide range of composition. With 60 to 65 pct Be

Jan 1, 1951

By P. M. Robinson, M. B. Bever

The heats oj formation at 273°K of the compounds CdTe, I)z2Te, InTe, In2Te3. In2Te5, SrzTe, and PbTe have been rleasrred in a liquid metal solutiotz caloritrete? 1.t1itlz bismuth as solvent. The?, are iterpretecl in yelation to tlze stability and bonding of the cott/pozltzds. Tile heats of fusion atzd the melting- points of tlze cotlzpounds InTe and Itzz,Te3 1lcti.e been measured in a cotrslant-temperature gradient calorimeter. The entropies of fusion are disc,ztssecl in YIIIS 01. the degree of order in the solid at the melting point. THE heats of formation of the tellurides of cadmium, indium, tin, and lead have been measured as a continuation of research on the thermodynamic properties of compounds of tellurim.' The tellurides of these metals were selected with a view to examining the relation between the heat of formation and the position of the metal in the periodic system. The elements cadmium, indium, and tin are in the same period and tin and lead are in the same group of the periodic system. The tellurides of indium are of special interest because four compounds, In2Te, InTe, In2Te3, and InzTe5, occur in this system. The available information on the heats of formation of the compounds investigated consists of values for CdTe, SnTe, and PbTe derived from electromotive-force measurements,J a value for CdTe obtained by tin solution alorimetr, and values for InTe and In2Te3 determined by combustion calorimetry.5 These values, however, refer to various temperatures ranging from 273' to 673°K and some of the reported error limits are large. Liquid metal solution calorime-try may be expected to yield more accurate values for the heats of formation than electromotive-force measurements or combustion calorimetry. The heats of fusion and the melting points of the compounds InTe and In,Te3 were determined in a constant-temperature gradient calorimeter. No published information appears to be available on the heat of fusion of these compounds. The results reported here give an indication of the degree of order in the solid compounds at the melting point. 1) MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Samples of the compounds SnTe and PbTe were obtained from the Westinghouse Research Laboratories and samples of the compound InTe from Lincoln Laboratory, Massachusetts Institute of Tech- nology. Additional samples of the compounds InTe, SnTe, and PbTe and samples of CdTe, In2Te, In2Te3, and In,Tes were prepared from 99.995 pct Cd (Baker Chemical CO.), 99.999+ pct In (American Smelting and Refining Co.), 99.99 pct Sn (Baker Chemical Co.), 99.999+ pct Pb (Fisher Scientific Co.), and 99.999+ pct Te (American Smelting and Refining Co.). Stoichiometric amounts of the component elements were melted in sealed, evacuated Vycor tubes. The melts were held at approximately 100°C above the liquidus for about 16 hr and shaken repeatedly. The melts of the compounds In2Te and InzTe5, which form by peritectic reactions, were quenched into iced water. The melts of the other compounds, which have congruent melting points, were slowly cooled to room temperature. The samples were then annealed for 5 days at approximately 50°C below their respective solidus temperatures. Metallographic examination did not reveal any evidence of second phases or segregation. At least two batches of each compound were prepared. Samples from each batch were used in determining the heats of formation and, in the cases of InTe and In,Te3, the heats of fusion. The Heats of Formation. The heats of formation at 273°K of the compounds were measured by metal solution calorimetry with liquid bismuth at 623" as solvent. In this technique, the heat of formation is determined from the measured heat effects on dissolution of the compound and of a mechanical mixture of the component elements. The difference between these heat effects adjusted for changes in the composition of the bath gives the heat of formation at the temperature from which the samples are added to the bath (273°K). The experimental technique and method of calculation have been described in detail elsewhere.= It should be emphasized that the reported heats of formation depend on the thermodynamic data used in calculating the heat effects for the calibration additions. In the present investigation, the calorimeter was calibrated by adding pure bismuth at 273°K to the bismuth bath at 623°K. The reported heats of formation are based on a value of 4.96 kcal per g-atom for the difference in the heat contents of bismuth at 623" and 273". If a new value for this quantity becomes available, the reported results may be adjusted in direct proportion. The concentration of solute in the bath at the end of a calorimetric run did not exceed 1.7 at. pct and was usually less. In this range, the heat effect on dissolution of the solute was a linear function of the concentration of solute. In determining the heats of formation of the compounds in the system In-Te, a few runs were carried out in which two neighboring compounds such as InTe and In,Te3 and the corresponding mechanical mixtures of the components were added to the calorimeter. The

Jan 1, 1967

By Enrique Hauser

FiRE-damp is a mixture of methane with other inert gases or combustible gases. The inert gases in question are carbonic acid, water vapor, nitrogen, etc. The combustible gases are hydrogen, ethane, etc. The study of the properties of fire-damp, therefore, becomes a study of the properties of methane and the influence on its properties of the different gases we have mentioned. Characteristic Properties of Methane 1. Respirability.—Methane being a paraffin is characterized by its weak chemical affinities. Prom the physiological point of view one could substitute it for nitrogen of the air at least momentarily, without experiencing any difficulty in breathing the mixture consisting of 21 per cent. 02 + 79 per cent. CHI. I have tried this on myself, making the gas exhaled from the lungs burn subsequently in a Bunsen burner.' From the chemical point of view, this weak affinity permits the gas to be burned in certain circumstances with hydrogen and oxide of carbon in an oxygenated mixture, with the result that the last two gases achieve only a fractional combustion. This practice has been utilized with success in the methods of analysis which I have perfected and which I describe later in this paper. 2. Retardation of Flashing Point.—A characteristic property of methane is its retardation of flashing point, noted by Davy in 1816 and studied by Mallard and Le Chatelier in 1883.2 Taffanel and Le Floch have recently confirmed these results.8 Let us recall the nature of this retardation: When a mixture of combustible gases with air or with oxygen is

Jan 1, 1916

By Dever C. Ashmead

Anthracite was first mined in the Wyoming Valley and sold as an article of commerce in 1808. As some preparation has always been necessary to make it ready to burn, the preparation of anthracite must date back over a hundred years. Two vital factors have determined to a large extent the degree and the method of anthracite preparation. These are, first, the character of the beds worked and the methods by which they are mined and, second, the equipment used and practices followed in the burning of the coal. It is not the intention here to go deeply into these phases of preparation as a paper of no mean length could be prepared on the history of either. Rather, the intention here is to point out the main considerations and to show the influence they have exerted on the preparation of anthracitc. Mining Methods and Their Relation to Preparation In the beginning of the nineteenth century, the coal beds were virgin with the possible exception of some outcroppings that had been worked, to a slight extent, by the Indians. It is known that the American aborigines had a, knowledge of the use of this fuel, because when the Wyoming Valley was purchased from them, in 1754, they mentioned the fact that, by selling the land, they would lose their coal. Real mining of anthracite began about 1808 when Judge Jesse Fell, of Wilkes-Barre, discovered that the "common stone coal of the valley" could be burned in an open grate. For some years thereafter mining was conducted near the surface. The working p1aces were driven narrow; only the best of the coal was selected and the remainder was left in the ground. Only the lumps could be used, as no market existed for other sizes. As time passed, however, it became necessary either to go farther into the ground or to widen the working places. When these places were widened, falls of roof were apt to occur, making it necessary

Jan 1, 1922

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By AIME AIME

THE autumn is the time that nearly all the special groups within the broad field of the Institute&apos;s activitives chose for their own special meetings. The big annual meeting in New York in February has its own special advantages, but to realize them involves sacrificing others. A meeting of a smaller group with the subjects brought up for discussion much more closely limited to a single field of interest has some advantages that a big general meeting cannot possibly have. And so the custom has gradually developed of having these smaller meetings in the autumn, at con¬venient places, so the men will not have to travel too far from the job to be present. Sometimes the meetings have for their field of interest a single phase of mineral technology, and are called divisional, and at other times they cover a diversity of topics that are locally important in that geographical area, and are then called regional meetings. Of the five meetings to be held this fall, four are divisional and one regional. Two of the divisional meetings are to be held in the same place at the same time, but with programs so arranged that they do not conflict.

Jan 1, 1930

"The reduction works of the Boston & Montana Reduction department, near the north end of this dam is one of the reduction plants belonging to the Anaconda Copper Mining Company, the other being at Anaconda. These works employ about 1,100 men and have a capacity of about 3,800 tons of crude ore per day. This plant is now being remodeled to embody results of experiments and investigations which have been made with a view to more economic.al treatment of ores. A brief description of the plant as it will be after the remodelling is as follows:Concentrator Department: Consists of six units or sections, each section treating from 550 to 600 tons of crude ore per day. This department is not being. remodelled at the present time. A concentrating process, however, has been developed and partially installed in the old mill, and an experimental section embodying this concentration process has also been installed at the concentrator at Anaconda."

Jan 1, 1913

By David C. Jonson, W. Bruce MacKenzie, Arthur A. Bookstrom, Vaughn E. Surface, Neil K. Muncaster, Stewart R. Wallace

In mid-Tertiary time a wet silici-alkalic magma penetrated the Precambrian rocks of what is now the Tenmile Range of Central Colorado and formed the Climax Stock. The stock is a composite one and was intruded in four separate irruptions, each giving rise to a major hydrothermal event. The first three of these produced large stockwork ore bodies that cap and flank the tops of their respective source intrusives; the fourth, and last, yielded almost no commercial mineralization. The ore bodies and their related zones of alteration are circular to ring-shaped in plan and arcuate in section. The different phases of the stock are so positioned with respect to each other that many of the circular and arcuate zones of mineralization and alteration overlap or are juxtaposed. Evidence of a time separation between the different ore bodies is found in certain dikes that were intruded between periods of mineralization and are well mineralized in one ore body but are barren in another. If it is assumed that the parent magma at Climax contained 10 per cent "water," that the "water" contained 0.1 grams per liter of molybdenum, and that the processes of extraction were 100 per cent efficient, then approximately 10 cubic miles of magma would be required for the formation of each ore body. The volume requirements, taken in conjunction with the cross-sectional areas of the different phases of the stock to explored depths, suggest to the authors that each magma chamber was columnar, extended to a depth of thousands of feet, and was connected with a much larger master reservoir. The repetition of similar intrusive, structural, and hydrothermal events, indicates periodic tapping of this reservoir. A regular chemical evolution of the parent magma is suggested by the systematic change in metal ratios and differences in the sites of deposition, relative to the source intrusive, in each of the four separate igneous hydrothermal stages. The preparation of ground was due to changes in magmatic and/ or hydrothermal pressures within the igneous-hydrothermal columns; small, repeated, up and down movements of the rock enclosing the tops of the columns formed the stockwork fractures into which the mineralizers penetrated. The forceful emplacement of each successive phase of the Climax Stock resulted in a slight doming and rotation to the westward of the earlier-formed geologic features. Postore normal displacement along the Mosquito fault is estimated at about 9000 feet. Part of one ore body was cut by the fault and lies at depth below the Paleozoic sedimentary strata on the hanging wall. On the footwall side of the fault, subaerial erosion and glaciation removed a large part of one ore body and uncovered the top of a second.

Jan 1, 1968

By E. Hein, R. A. Dodd

The fatigue softening of prior strain-hardened poly crystalline copper has been determined by measuring changes inflow stress resulting from fatigue treatments. Tensile fatigue does not soften the metal, while the softening due to reversed stress fatigue depends on the extent to which fully reversed stressing is approached. True tensile fatigue is shown to be possible only in the case of long wire specimens. Annealing following fatiguing of strain-hardened metal shows that tensile fatigue is very effective in modifying normal recovery and recrys-tallization. OBSERVATIONS by Ludwik and Scheu,&apos; Kenyon,&apos; Polakowski and Palchoudhuri, Kemsley, and Broom and Ham,596 have shown beyond doubt that strain-hardened metals are softened by reversed-stress fatigue. To some extent the softening might be associated with a rearrangement of dislocations, but the results of Broom and Ham5 on the temperature dependency of the fatigue hardening of annealed copper, and those of McCammon and Rosenberg7 on the partial recovery at 100&apos;C of fatigue-hardened copper suggest that point defects may be involved. Since lattice vacancies are the only species of point defect present in appreciable quantities in thermody-namic equilibrium, most attention has been accorded them in the various theories advanced to explain hardening and softening effects resulting from fatigue. Precise mechanisms remain uncertain, and while some effects may be due to single vacancies, defects arising from vacancy clusters may also contribute to the changes in properties. All types of plastic deformation result in point-defect formation, one frequently invoked formation mechanism involving the nonconservative motion of jogs formed by the intersection of, for example, mixed dislocations. But since fatigue deformation is thought to be a particularly effective way of forming point defects, additional mechanisms peculiar to fatigue must be sought. One possibility is that jogged loops contract during the unloading cycle to give rows of vacancies. A local high-vacancy concentration could conceivably promote polygonization and recovery by climb, and, therefore, could explain the fatigue softening of strain-hardened metals under appropriate conditions of temperature. Conversely, the experiments by Broom and Ham6 on the fatigue hardening of copper single crystals involving subsequent tensile testing of previously fatigued specimens, resulted in the observation of distinctly lowered yield points. This could be due to vacancy atmospheres associated with dislocations, possibly augmented by jogs on dislocations. In addition to the yield-point phenomenon, a post-yield hardening was observed, with a temperature-dependence resembling the friction-hardening of irradiated metals,9 this again suggesting a point-defect mechanism. An important development in this field has been the observation,10 by transmission electron microscopy, of high concentrations of prismatic loops in fatigued aluminum. By analogy with quenched aluminum filmso11 it seems certain that these loops originate in the collapse of vacancy clusters formed during deformation. Metals, such as copper, having a relatively low-stacking fault energy would tend to produce Frank sessile loops (in practice tetrahedral defects with stacking faults on all (111) planes) rather than the glissile prismatic loops observed in aluminum. The manner in which these various defects affect the different aspects of fatigue behavior has not yet been fully investigated. The present work was designed principally to indicate whether tensile fatigue gives rise to hardening and softening effects similar to those associated with reversed stress fatigue, and with the hope of providing additional information on the contribution of point defects to fatigue deformation. Despite the uncertain ty often associated with the interpretation of resistivity data, i.e., the relative contribution of stacking faults and other defects, such measurements are conveniently employed to study point defect pheno-

Jan 1, 1962

By R. I. Parsons, M. B. Standing, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By M. B. Standing, R. I. Parsons, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By AIME AIME

FREE competition, long the controlling ideal of domestic trade within the United States, has had the fundamental geographical advantage of functioning in the world&apos;s largest area of unrestricted commerce. Goods moved back and forth across state lines, unimpeded by customs, and industrial operations have developed rapidly to meet the expanding needs of a pioneer country richly endowed with natural resources. Fifty years ago, antitrust laws were adopted to protect the competitive private enterprise principle. It became illegal for one person to combine with another to restrain trade or commerce among the several states or with foreign nations. The original legislative measures defining this philosophy were the Sherman Act of 1890 and the Clay- ton Act passed in 1914. The development of Europe and other parts of the world was influenced by different conditions which led to a different theory of trade. Here were many small nations, with limited natural resources and a thin market, and they attempted to protect their national economy by tariff walls. International business arrangements for the purpose of diminishing the ups and downs of the more competitive system --crux of the modern cartel operations-seemed a logical device to stabilize production and guard the interests of both workers and consumers. European governments as well as European industrial interests became convinced that if com- petition could be held in bounds the danger of business depressions and un- employment could be reduced.

Jan 1, 1944

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By Cloyd M. Smith

A FEW years ago, the Ventilation Committee established the practice of presenting one topic each year for discussion at the annual meeting. The practice has met good response on the part of committee members and I suggest that it be continued. The topic chosen for this year, "Underground Anemometry," is a topic which has bothered me for more than 20 years. It seems to me that the coal industry is content to rely on slipshod methods for measuring the rate of flow of air underground, so I prefaced my discussional charge to committee members with the statement that I regard air measurements made in the usual way, with hand held anemometer, as no good. Agreements and disagreements came in from more than a dozen engineers, some of whom are with operating companies, coal and metal; some with manufacturers; others with government agencies.

Jan 1, 1949

By Robert H. Richards

The adaptation of European methods of concentrating ores to suit the conditions of this country has followed the lines that simplify machinery, diminish labor and increase capacity. Noteworthy instances are the substitution of hydraulic classifiers for the last one or two trommels in the series, and the substitution of a distributing-tank for the slimes in the place of the Spitzkasten. The question may be fairly asked, At what point do losses become serious in consequence of these changes? It is to study this question that the investigation herein described has been undertaken. After the losses are located and the methods of stopping them are pointed out, it will then lie with the individual mill to decide whether or not the plans proposed will save suficient value to warrant their adoption. In the discussion of sorting followed by sizing, as the terms are used in this paper, me have to deal with the preparation of slimes by the Spitzkasten for subsequent washing upon the slime-table. The Spitzkasten, or pointed box, is an inverted hollow pyramid, generally of wood, usually with four faces or sides coming together in a point below. The sides can have, according to Rittinger, a minimum angle of slope of 50" with the horizontal. The feed-water carrying fine slimes (less than 0.01 inch, or 0.25 mm. in diameter) for treatment is fed at one end and carefully distributed over the whole width. The outlet is over the opposite end. The water-current passes direct from inlet to outlet, and has usually been regarded as a surface-layer pass-

Jan 1, 1898

By A. Gemperle

Electron diffraction and transmission electron microscopy on foils at room temperature were used to investigate the ordering of Fe-Si alloys containing 10 to 23 at. pct Si. A certain degree of DO3 order was found in all alloys. With the exception of the lowest silicon concentration for which the antiphase domains could not be clearly resolved, the alloys have a domain structure of two-domain type with boundaries having 1/4a01<111> displacement vectors for less than 12.3 at. pct Si and with boundaries having 1/2 a0<100> displacement vectors for more than 12.3 at. pct Si. The alloys with 12.3 at. pct Si have a domain structure consisting of fine domains with 1/2a&apos;o<100> boundaries within much larger domains with 1/4a&apos;o<111> boundaries. The development of these structures can be explained by transition of the alloy from the disordered state into the B2-type order and then into the D03-type order by the mechanism proposed previously for the FeSAl alloys. The existence of the B2 structure in the lower part of the investigated concentration range reported in some articles can be explained by fine domains with 1/2a&apos;o<100> boundaries formed by several disordered planes within large domains with 1/4a&apos;o<111> boundaries. The ordered structure predicted by the theory —with practically no domain boundaries —is found in the alloys having 12.3 at. pct Si where it develops in the B2 structure region. ORDERING in Fe-Si alloys was first studied by phragmenl who found that beginning with 13 at. pct Si the DO3 (Fe3Si) superlattice reflections appear in the diffraction patterns. The equilibrium diagrams constructed later by corson2 and Haughton3 from various measurements proposed the existence of a homogeneous solid solution (a phase) in the range from 0 to 25 at. pct Si. Jette and Greiner4 and Farquhar et al.5 measured the relation between lattice parameter and composition and they considered the break in the curve at 9 to 10 at. pct Si to be caused by the ordered solution a"(Fe3Si). Glaser and Ivanick6 Determined critical ordering temperatures of the alloys containing from 10.9 to 27.9 at. pct Si from the measurement of the electric resistivity of quenched samples. In all cases the critical temperature was lower than the melting point and it was highest for 25 at. pct Si. Lihl and Ebel7 measured the lattice parameter curves at various temperatures up to 1000°C. The region between two breaks on these curves, corresponding to 10 to 12.5 at. pct Si at room temperature, was considered by them to be two-phase (a + a"). They concluded by extrapolation of the measured values that a" in the alloy having 25 at. pct Si is stable up to the melting point. Davies8 studied superlattice reflections in the X-ray diffraction patterns of an alloy containing 8.7 at. pct Si. He found the B2 structure and short-range order in the slowly cooled samples and the DO3 A. GEMPERLE is Research Scientist, Institute of PhysicS, Czechoslovak Academy of Sciences, Prague, Czechoslovakia. __Manuscript submitted January 2, 1968. IMD structure in the quenched and annealed samples. This investigation first reports the presence of the B2 structure, phase a&apos;: in Fe-Si alloys. Meinhardt and krisement9,10 also found its existence in Fe-Si alloys by neutron diffraction. No order was detected by them in the alloy containing 8 at. pct Si. The onset of B2 order was observed at a composition of 9.2 at. pct Si. They found almost perfect B2-type order with partial DO3-type order at room temperature in the 10 to 12.5 at. pct Si range and almost perfect DO3-type order in the 12.5 to 25 at. pct Si range. They established the critical temperatures Tc of both the structures through measurement at higher temperatures. The critical temperature for the B2 structure was found to be always higher than the critical temperature for the DO3 structure of the same alloy. They extrapolated the curves of the critical temperatures and concluded that the alloys with more than 17 at. pct Si have the B2 structure up to the melting point and the alloys with more than 23 at. pct Si have the DO3 structure up to the melting point. The results of Meinhardt and krisement9,10 were confirmed by Dokken&apos;s measurement" of the temperature dependence of the electrical resistivity in the 10.8 to 15 at. pct Si range. On the other hand chessin12 detected by X-ray diffraction a considerably lower degree of order in the 12.7 at. pct Si alloy. ANTIPHASE DOMAIN STRUCTURE IN ALLOYS WITH B2- AND DO$-TYPE ORDER The ordered structures B2 and DO3 can be described in terms of a subdivision of the bcc lattice into four fcc sublattices with a parameter double that of the bcc lattice. Following Marcinkowski13 we will label them I. 11, 111, IV. The B2 structure in the AB alloy is formed by placing A atoms on sublattices I and II and B atoms on sublattices III and IV. In a non-stoichiometric perfectly ordered alloy having concentration (A) > (B), A atoms occupy sublattices I and 11. and A and B atoms distributed at random occupy sublattices III and IV. The DO3 structure in an A3B alloy is formed by placing A atoms on sublattices I, 11, and 111, and B atoms on sublattice IV. In a nonstoichiometric, perfectly ordered alloy having concentration (A)/3 > (B), A atoms occupy sublattices I, 11, and 111, and A and B atoms distributed at random occupy sublattice IV. As further shown in Ref. 13, two types of domains are possible in the B2 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4 a&apos;o<ll1> only. Four types of domains are possible in the DO3 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4a&apos;o<111> and 1/2a&apos;o<l00>. Bethe14 suggested on the basis of theoretical considerations that in a structure with two sublattices at low temperatures only one domain should be present in the whole crystal at equilibrium. Similarly Bragg15 concluded that at low temperatures the domain struc-

Jan 1, 1969

By W. T. Olsen, R. Ulcer

WHEN a liquid alloy freezes, the solid first formed usually differs widely in chemical composition from that last formed, so that there is segregation in the alloy as cast. For example in the copper-nickel system (fig. 1) the first solid formed from a liquid containing 55 atomic pct Cu may contain as little as 38 pct Cu, while the last must contain well over 55 pct. Three factors may act to decrease segregation from the maximum possible. 1. Diffusion in the cooling solid tends to make the phase homogeneous, decreasing segregation. This may be important at slow rates of cooling. 2. Segregation is impossible without diffusion in the liquid. At extremely rapid rates of cooling there may not be enough time to allow maximum segregation. 3. Supercooling delays nucleation to temperatures well below the liquidus thereby decreasing segregation. Hence the first nucleus in the copper-nickel system may contain well over 38 pct Cu. At sufficient supercooling the first nucleus may form below the solidus, in which case there is no reason to expect any segregation whatever. From these considerations, we could predict that at sufficiently low rates of cooling the alloy would be unsegregated because of factor 1 and at sufficiently high rates of cooling there should also be no segregation because of factors 2 and 3. Considerable segregation should occur only at intermediate rates of cooling. We have demonstrated experimentally that segregation can be completely suppressed by rapid rates of cooling. For the alloys studied, however, these rates are too great to be attained in any commercial practice. An alloy of 55 atomic pct Cu, 45 atomic pct Ni was frozen by cooling at varying rates. The degree of segregation in the solid was determined by X-ray diffraction photographs. Slow rates were obtained by slowly cooling the furnace containing the liquid alloy; fast rates by pouring or ejecting droplets of the alloy into water or iced sodium hydroxide solutions. The cooling rate of the droplets can be cal-culated from their dimensions by assuming reason- able values of thermal conductivity.&apos; The experi-ments were repeated with an alloy of 16.5 pct Cu and 83.5 pct Au. A single experiment also showed a 50 atomic pct Bi-Sb alloy had no segregation at the most rapid quench. The position of back-reflection X-ray diffraction lines is a highly sensitive function of the lattice constant, which in turn depends on the chemical composition of the phase. A phase of varying composition will give broad diffraction lines. By measuring the edges of these lines and making suitable corrections for intrinsic line width, it is possible to determine the range of lattice constants represented. These can be converted to chemical compositions from a lattice constant vs. composition curve. Results are shown in table I. In the copper-nickel system the greatest segregation is found at the slowest cooling rates, where the lowest percentage of copper theoretically possible is found. In the copper-gold system, on the other hand, the degree of segregation is decidedly less at the slowest rates of cooling, being greatest at 11,100°C per sec. At no rate is the theoretically lowest percentage of copper (12 pct) found. At the rates of cooling found in sand and die castings the degree of segregation is large and depends little on the rate of cooling. Acknowledgment Most of the material in this paper is abstracted from a thesis presented by William T. Olsen, Jr. in 1948 in partial fulfillment of the requirements for the degree of Master of Science at the University of California.

Jan 1, 1951

By E. W. Enqelmann

DURING January, 1933, burlap or coco matting was placed in the bottom of launders handling various products of the flotation plant of the Magna mill of the Utah Copper Co., with the hope of increasing the total recovery of gold. This was soon followed by placing various materials, such as coco matting, cotton twill, and common 10-oz. burlap on the bottom of the main tailing launder. The burlap was found to be the most economical material to use. The test was first conducted in an old wooden launder, 40 in. wide and 2000 ft. long, with 10-oz. burlap fastened

Jan 1, 1935

By Wilfred P. Sykes

AT intervals in the course of history an event occurs which, though scarcely heeded at the moment, marks in retrospect the beginning of a new era in some one field of human activity. Such a happening is perhaps more readily spotted in the field of technology than in other realms of human endeavor. Here the span of years is relatively short and the records have been kept with some degree of precision. In the current scene of our social and economic drama the art and science of metallurgy is playing a major role. Off stage will be found the metallurgist in one guise or another aiding, he trusts, in the development of processes and products which will contribute to the happiness of his fellow men. The results of his efforts appear in the form of metallic substances known as alloys built up from any two or more of the wide variety of metals which have been extracted from the mineral deposits in the earth&apos;s crust. An alloy by virtue of its inherent physical properties may seem ideally suited for human use in a special way but until this material can be produced economically it will fail to attain a place of prominence as an article of commerce. In fact many commercial alloys are being continually replaced by new or modified compositions better suited to meet the increasingly severe demands of industrial service.

Jan 1, 1939