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By W. A. Vine

When a hole is made in a stressed solid, such as rock pierced by mine openings, equilibrium of the solid is destroyed. To restablish that equilibrium the stress condition in the rock surrounding the opening becomes rearranged. This rearrangement may or may not develop local stresses in the vicinity of the opening which exceed the elastic strength of the rock. Since stability of the opening depends, therefore, on the strength of the naturally occurring rock surrounding the opening, this rock is an engineering material of construction, and all rock affected by the associated opening or system of openings may be considered a structure. The term invert is chosen to describe the formation of the structure built from the inside, as it were, and a consequence of mining rather than an entity built for a purpose. By definition, an invert structure is formed when openings are made underground and is com- posed of that material on the solid side of a rock-air interface wherein the stress condition is affected by the associated opening or system of openings. The shape of an invert structure is never clearly defined; the skin of the structure may be mapped, and even described, but the boundary of the structure within the solid rock mass must be arbitrarily set.

Nov 1, 1955

By R. W. Newcomb

THE constancy of calibration, and to a great extent the life, of a thermoelement is dependent on the suitability of the primary protecting tube in which the wires are mounted, particularly when used at high temperatures. An ideal thermocouple protecting tube would be com-posed of materials that would not contaminate the thermoelement wires contained in it-one that would remain absolutely gas-tight ,it all temperatures of usage, that will not be attacked by gases, or other surrounding agencies, that is not destroyed by heat, that withstands sudden and extreme temperature changes, that affords a high degree of mechanical protection and does not deform at high temperatures, that is a good heat conductor and obtainable in small diameters so as to keep down lag factors. It has not yet been possible to produce tubes of any known mate-rials that will meet all of these conditions. In selecting protecting tubes, therefore, one should be chosen the characteristics of which best fit it to the particular conditions of usage. Frequently conditions are such that two tubes have to be used, a primary gas-tight protecting tube inside of a secondary protecting tube, because certain agencies will attack the primary gas-tight tube unless it is guarded by the outside tube.

Jan 9, 1919

By George S. Rice

DEFINITE data on the amplitude and effect of ground movement in specific mineral formations, caused by various methods used in the mining of ores, coal, and nonmetals, or in the extraction through wells of petroleum, sulphur, and soluble salts, are increasingly needed because of legal liabilities from damage to overlying or adjacent properties, and growing concern as to the conservation of national mineral resources. Not since the committee was established in 1923 has it been so difficult to get technical papers giving ground movement and subsidence data from specific mine operators. The reasons given, as above indicated, are pending or threatening lawsuits. There are three major objectives in ground movement and subsidence studies : (1) Maximum recovery of a mineral resource. (2) Minimizing damage to surface structures, highways, railroads, and agricultural lands caused by caving or subsidence, which may in some situations, as along the Gulf of Mexico shore, cause flooding by surface waters. (3) Lessening damage to overlying or adjacent mineral by back-filling of mine excavations as completely as possible.

Jan 1, 1940

By C. F. Baes, H. H. Kellogg

The effect of dissolved sulphur on the surface tension of liquid copper has been measured by a sessile-drop method at 1120°C. Sulphur is highly "surface active" in liquid copper; the surface tension lowering is about 650 dynes per cm for a sulphur content of 0.6 pct. The degree of adsorption of sulphur on the liquid copper surface has been calculated, and various models of the surface layer have been tested against the results. THE science and technology of surface chemistry and physics at room temperature are relatively advanced, and the engineer possesses a background of information that allows him to predict and control many phenomena—such as frothing, emulsifica-tion, wetting of solids by liquids, flow through capillaries, adsorption, mineral flotation, penetration of porous bodies by liquids—which are related to the behavior at interfaces. Surface phenomena in high temperature systems are probably of equal importance to the metallurgist and ceramist, but at present are incompletely understood. Frothing of liquid slags, penetration of refractories by liquid metals and slags, infiltration of powder metallurgy "skeletons" by liquid metals, bonding of metals to ceramic oxides in the manufacture of "cermets," wetting of one metal by another for purposes of soldering and welding, are but a few of the many phenomena of metallurgy that are controlled by surface behavior. Concerning the most elementary of surface properties—the gas-liquid surface tension—the existing data on liquid metals are inadequate. For the surface tension of "pure" metals the results of different investigators differ by 10 or 20 pct. The role of surface-active agents in liquid metals is relatively unknown, and it is not unlikely that the discrepancy in the values for the surface tension of pure metals is due to the presence of traces of surface-tension-lowering impurities in the samples. Based on analogy to room-temperature systems, the highly surface-active impurities in liquid metals should be elements or compounds of limited solubility in the liquid metal and possessing considerably weaker in-termolecular bonding forces than the metal itself. The nonmetals of the V, VI, and VII groups of the periodic table might be expected to act in this way. The experimental work in this paper represents a study of the surface tension of pure liquid copper in hydrogen at 1120°C, and the effect of dissolved sulphur (which is a strongly surface-active agent in liquid copper) on the surface tension of copper. The Gibbs equation has been applied to the results and an attempt made to correlate the surface tension behavior with two models of the interfacial layer. The sessile-drop method for surface-tension measurement at high temperatures which was used in this investigation has been described by several investigators.1,2 It involves the measurements of the dimensions of a stationary liquid drop on a horizontal surface. From these dimensions and the liquid density, the surface tension of the liquid may be calculated either by means of various approximate formulas, or more accurately by means of the Bash-forth and Adams tables.- or liquid drops which exhibit a contact angle greater than 90°, by far the simplest dimensions to measure are those indicated in Fig. 1, i.e., the diameter of the maximum horizontal cross section (2X) and the maximum height (Z) above this plane. In order to calculate the contact angle and the volume of the drop, the diameter at the base of the drop (2a) and the total height (h) also must be measured. Upon investigation of the literature, the authors failed to discover a concise statement of the accuracy of the method when used in conjunction with the Bashforth and Adams tables, hence a careful examination of the tables was made and the curve shown in Fig. 2 was constructed. The "error factor," plotted as the ordinate, is the factor by which the

Jan 1, 1954

By B. D. Cullity

A distribution of residual stress after plastic elongation is proposed, in which the bulk of the material is strained in compression and a very small portion in tension, This distribution is shown to account both for the X-ray observations and for the effect of plastic straining on magnetic losses in silicon steel. The regions left in compression are tentatively identified with the interiors of the sub-grains revealed by the electron microscope. THIS paper is concerned with the general problem of the nature of the residual stress which is produced in metals by plastic elongation. A particular stress distribution will be suggested which accounts for the main X-ray diffraction observations which have been made. It will also be shown that certain magnetic measurements made on silicon steel can be understood in terms of this stress distribution. X-RAY OBSERVATIONS Uniform straining of a crystal lattice (macro-strain) causes a diffracted X-ray beam to shift its position, and nonuniform straining (microstrain) causes line broadening. If a bar of metal is plastically elongated in the longitudinal x direction and then unloaded, diffracted X-ray lines are observed to be both shifted and broadened.'-= Although the observed line shift indicates the presence of macro-strain, experiments have shown that no macrostrain, in the usual engineering sense of the term, exists.5"7 For example, removal of a layer from one surface of a stretched and unloaded bar does not produce curvature in the remainder of the bar 5'7 Fig. 1 shows the variation of lattice strain in the x direction, as determined from X-ray line shifts, with the applied stress in the same direction. The curve ABC is the normal stress-strain curve of the material, AB being the elastic portion and BC the plastic. In the elastic region AB, the strain measured by X-rays, called the lattice strain, and the strain measured mechanically are both proportional to the applied stress, and both return to zero when the applied stress is removed. Above the elastic limit the lattice strain would be expected to continue to increase along the line BD. Actually, it increases less rapidly with respect to stress, or even decreases, as shown by BE. If the applied stress is then decreased, the lattice strain decreases along EF, which is parallel to AB. As a result, there is a compressive residual lattice strain FA after unloading. STRESS DISTRIBUTION. Since a stretched and unloaded bar does not contain macrostress, it follows that the observed line shift must be due to a special distribution of mi-crostress. Such a distribution is shown in Fig. 2, which shows the variation of the stress u, across a stretched and unloaded bar. The material is assumed to consist of two kinds of regions: regions C, stressed more or less uniformly in compression, comprising the bulk of the volume of the material and responsible for the observed diffrac-

Jan 1, 1963

By C. S. Finney, John Mitchell

The introduction of ovens for the production of metallurgical coke is believed to be due to L. L. Norton who operated an iron foundry in the vicinity of Connellsville, Pa. Persuaded by his foreman, an English immigrant named Nickols from Durham, L. L. Norton put up a 12-ft square oven which produced coke in 1833. The coal used was taken from a local mine at Mounts Creek. The oven seems to have been used in conjunction with the customary method of coking in mounds. It was in the Connellsville district also, in 1841, that two carpenters, Provence McCormick and James Campbell, formed a partnership with John Taylor, a stone mason, for the manufacture and sale of oven coke. The task of the mason was to construct the ovens, while the carpenters were to build the arks by which the coke could be taken by water to the market at Cincinnati. The following account of the enterprise was given by McCormick: "James Campbell and myself heard in some way that I do not now recollect that the manufacturing of coke might be made a good business. Mr. John Taylor, a stone mason, who owned the farm on which the Fayette coke works now stand, and who was mining coal in a small way, was spoken to regarding our enterprise, and proposed a partnership-he to build the ovens and make the coke and Mr. Campbell and myself to build a boat and take the coke to Cincinnati, where we heard there was a good demand. This was in 1841. Mr. Taylor built two ovens. I think they were about 10 feet in diameter. My recollection is that the charge was 80 bushels. The ovens were built in the same style as those now used, but had no iron ring at the top to prevent the brick from falling in when filling the oven with coal, nor had we any iron frames at the mouth where the coke was drawn. The top and mouth had to be repaired when they fell in. In the spring of 1842 enough coke had been made to fill two boats 90 feet long-about 800 bushels each-and we took them to Cincinnati down the Youghiogheny, Monongahela, and Ohio, but when we got there we could not sell. Mr. Campbell, who went with the boats, lay at the landing some two or three weeks, retailing out one boatload and part of the other in small lots at about 8 cents a bushel. Miles Greenwood, a foundryman of that city, offered to take the balance if he would take a small patent flour mill at $125.00 hi pay, which Mr. Campbell did. He had it shipped here. We tried it, but it was no good, and we sold it to a man in the mountains for $30.00, and thus ended our coke business." So successful did the coke subsequently prove to be in use that the three partners were asked to deliver more. Evidently they had had enough of the coke business, however, for they refused to have anything more to do with it. Few ovens were built between 1841 and 1855, and it is reported that in the latter year, "there were only 26 coke ovens along the river above Pittsburgh". Successful coke makers of these years included Mordecai Cochran, Richard Brookius, and Colonel A. M. Hill. It was the use of coke in 1859 in the Clinton furnace erected by Graff, Bennett and Co. in a plant on West Carson Street, Pittsburgh, that brought the real beginning of the coke-iron era in America. Here the successful use of Connellsville coke as a blast-furnace fuel was demonstrated beyond all possible doubt, and from the year 1859 the coking industry expanded tremendously. The era of beehive coke ovens During the latter half of the nineteenth century and the early years of the twentieth, the major percentage of metallurgical coke produced in the United States came from beehive ovens. It was not until 1893 that the first battery of by-product ovens came

Jan 1, 1961

"The Washoe Smelter is situated about two miles east of the City of Anaconda. The smelter site includes about 240 acres and peculiarly adapts itself in topography to the efficient handling of material. By reason of its being on a hill side it is possible to make the level of delivery of the product of one building the level of the charge floor of the next succeeding one.THE ORES: The ore treated comes principally from the Butte district and is hauled by the Butte, Anaconda & Pacific railway, a distance of twenty-eight miles, in trains of fifty 50-ton bottom-dump cars to the railroad yards at East Anaconda. At this point these trains are• split up according to their destination,—that is, as to whether they go to the concentrator and sampling mill ore bins, or to the storage bins. In each case they are made up into trains of eight or sixteen cars, according to the size of engine to be used, and are carefully weighed before delivery to their respective bills.Some idea of the magnitude of the works may be obtained from the following figures:Amount of ore that can be treated in 24 hours…12,000 tonsLime rock from adjacent quarries…2,300 tonsCoke used…500 tonsCoal for reverberatory use…500 tonsCoal for power use…50 tonsWater, per minute, 35,000 gallons.Men employed in and around Anaconda, 3,000. Monthly payroll for above, $300,000.00."

Jan 1, 1913

By Walter Hull Aldridge

Much has been said about the foreseeable exhaustion of known mineral reserves-particularly in the United States. It is claimed that we are about to become a have-not nation insofar as certain essential minerals are concerned; and in this respect our position is often contrasted with that of the world as a whole, largely because we have drawn so heavily on our domestic resources during the last fifty years. As a matter of fact, the difference is not great if one takes a reasonably long-term view of the situation. No one denies that nature endowed the United States richer in mineral resources than any other equal area. It is granted that we have skimmed the cream of many kinds of minerals; but in a free international trade in minerals it would not be many decades before the richer deposits-at least the deposits easy of discovery throughout the world would be depleted to much the same degree as those in the United States today. For it is a fact that the problem of satisfying the needs of our industrial society for minerals is fundamentally worldwide in scope. The singular and significant attribute to all minerals is that there is but a single crop. Forests can be grown, but mineral deposits can be replaced only by finding new ones. Thus, one of the vital tasks of the mining engineer, the petroleum engineer, and the geologist is to find these new mineral resources. Another task is to devise means and methods for the exploitation of, at costs that are economic, low-grade deposits and those deeply buried in the crust of the earth. The first need, however, is to find the deposits in the ground. If the assumptions of those who today fear an early exhaustion of all deposits are valid, the outlook for continued material and social progress is gloomy indeed. I take a more optimistic view, for it is my belief that vast new sources of needed minerals will have come to light before our known resources are gone. The real question is whether the outside layer of the crust of the earth that is accessible to engineers contains adequate mineral deposits; and whether engineers can find those deposits. The answer must be based on geologic science, geologic fact, and mining history. Every continent, and almost every country, has yielded minerals of industrial utility in substantial quantity. Mineral deposits are widespread. Geologists know the conditions that were favorable to the occurrence of ores and the types of rocks in which various kinds of ores may ordinarily be found. They know that such rocks occur over broad regions of the earth's surface. They also know that in large areas rocks that are potential carriers of ores are covered and concealed by material of entirely different character. Such cover may consist of lava flows, layers of volcanic ash, or beds of material washed down from the surrounding mountains. Sometimes those covers are thick, sometimes relatively thin. But men well-qualified to pass judgment are sure that concealed deposits, large in number and in size, exist close enough to the surface to make exploitation practical. Only by actual penetration of the surface can this contention be proved, but to conclude otherwise would be to ignore the laws of probability and to deny the over-all consistency of nature. The task of probing the crust of the earth to determine the location of these deposits, and to obtain some notion of their size and quality, poses serious problems. However, they should not be beyond human solution. Much more research must be done in analyzing and explaining the laws of ore deposition. New tools, in the shape of techniques and methods and of mechanical and electrical devices and instruments, must be developed. But no reasonable person can doubt that these objectives will be achieved. As the need becomes increasingly pressing, scientists and engineers will supply the imagination and the ingenuity that will provide the solution. The time and effort thus far devoted to the development of methods for locating hidden ore bodies have been pitifully meager. Energetic investigation of the subject of applied geophysics is essential to the success of the mineral industry, and I have no hesitation in predicting that effective techniques will be found and successfully applied. Twenty-five years ago the petroleum industry

Jan 3, 1950

By J. H. Moran, E. E. Finklea

The pressure build-up technique is a recognized method of determining permeability from conventional drillstem tests. In this paper an effort is made to extend such techniques to the interpretation of data obtained from the wireline formation tester. Such a study is necessary because of the differences, for this case, in the magnitude of the flow parameters (rate of flow, amount of recovered fluids) and in the flow geometry (flow through a perforation vs flow across the face of the wellbore, etc.) involved in the solution of the equations of flow for compressible fluids. The perforation is replaced by a spherical hole, and the effect of the borehole is neglected, so that the flow can be considered to be radial in a spherical co-ordinate system. Arguments are presented to justify this idealization. Assuming single-phase flow, general relations between pressure and flow rate are developed for a homogeneous medium. The study is then extended to permeable beds of finite thickness. It is shown that the early stages of pressure build-up tend towards spherical flow, while the later stages tend towards cylindrical flow. The thinner the bed, the more quickly flow approaches the cylindrical model. The prevalence of thin beds in practical work makes this analysis quite important. Cases involving permeability anisotropy are treated. INTRODUCTION From wireline formation tester operation, two types of data are obtained: (1) the nature and amount of recovered fluids, and (2) the pressure history recorded during the test. A number of papers have been written dealing with the interpretation of formation production on the basis of the recovered fluids.'.' In general, the methods described have been quite accurate for both high- and low-permeability formations. The present paper will deal with an analysis of the pressures observed. An analysis of the pressure build-up curves obtained in hard-rock country has already been attempted on the basis of the formula proposed by Hor-ner. Although this approach has met with success in many instances, some questions have been raised as to its validity. It is the aim of the present study to place the analysis of pressure build-up in the formation tester on a firmer basis, from which more detailed methods of interpretation can evolve. Because of the great differences between the operation of the wireline formation tester and the conventional drillstem test, modifications are necessary in the interpretation. The major difference relates to the flow geometry. Once the flow geometry has been established other features such as multiphase flow, skin effect, afterflow, etc., well described in the literature, can be introduced. It will be assumed that the mechanical operation of the formation tester is already known to the reader.6 t will suffice here merely to state that the tester provides the means for taking a relatively small sample of the fluid immediately adjacent to the borehole, and for recording the subsequent pressure response. In comparison with conventional drillstem tests, the time required for a satisfactory pressure build-up response is much shorter, because of the relatively small quantity of fluid withdrawn by the wireline tester. This feature is highly desirable in the case of low-permeability formations. For an analysis of the pressure response within the formation, three simple flow geometries are considered— linear, cylindrical and spherical. The spherical and cylindrical flow geometries are most pertinent to the formation tester; therefore, they will receive the major emphasis. Since the configuration of the borehole and the perforation made by the tester complicate the flow geometry, it is necessary to allow for them in the drawdown response. However, because of the volume of formations contributing to the pressure-response, the details of the perforation shape are unimportant in the build-up period. Since relatively small amounts of fluid are withdrawn from the formation, in contrast to a conventional drill-stem test, a study of the "depth of investigation" and the significance of drawdown as well as build-up data will be included. Because the "depth of investigation" will be shown to be rather large, the effect on the build-up curves of the finite thickness of the permeable bed is considered. It is this consideration that leads to the importance of cylindrical flow geometry. Also included is a discussion of permeability anisotropy and its effect on the interpretation of the tester results. The pressure curves recorded by the formation tester will follow two general patterns, depending upon whether the formation is of high or low permeability. Fig. I (a and b) schematically illustrates these two responses. In Fig. 1(a), the high pressure recorded during fill-up of the tool is essentially the pressure differential across the choke in the system. In Fig. l(b), the flow rate is

By T. D. Jones

MUCH the same story can be told for the lead industry for the year 1945 as for the three previous years. In response to inquiries as to new developments, invariably the answer has been, "No new developments-our men either too busy with the man-power problem or trying to get production out." Time and efforts of industry have been concentrated for the most part on war or readjustment problems. Now that V-E and V-1 day have passed, the lead industry can justly be proud of its record in World War II. As in previous wars, lead played an important role and one of its most spectacular uses was in the production of the atomic bomb. We read that the part lead played was rather obscure, but as a protective agent, lead played a most significant role. "Since the materials in the Pile Plant are intensely radioactive, all storage and handling must be done behind thick concrete walls or lead shields. The material is never seen and all operations are auto matically controlled by a foolproof remote control system especially designed for this purpose." (Chews. & Met., Sept. 1945.) When our armies invaded the European theater of war and made a landing on Normandy beach, gasoline and oil for the motive power were furnished through miles of armored lead pipe. This amaz-

Jan 1, 1946

By J. M. Smith, D. Kunii, P. Adivarahan

Effective thermal conductivities were measured for seven samples of porous rocks through which gases or aqueous salt solution were flowing, parallel and countercurrent to the flow of heat. The results are analyzed in terms of the contributions of the solid and fluid phases to the total energy transfer. The solid contribution for the sandstone samples studied was found to be a Junction of the porosity and an effective thermal conductivity for the solid phase. The fluid contribution was a function of the Peclet number. Based upon the equations presented, the effective conductivity of the system can be estimated from the properties of the fluid, the flow conditions, and the porosity and pore-size distribution of the rock. INTRODUCTION Heat-transfer characteristics of porous media containing fluids are needed for the design and evaluation of thermal methods of petroleum production. The study reported here considers the problem of countercurrent flow of fluid and heat in sandstone rocks, and is a continuation of previous studies concerned with parallel and radial flow of energy and fluid in both rocks517 and beds of fine particles.6,10 In addition to these earlier works, Asaad,1 Kimura,4 Preston,8 Zierfuss and vlietll and waddams9 have reported effective conductivities for systems filled with stagnant fluids. There appears to be no published data on rocks through which fluids are flowing. The purpose of this study was to present such information and, particularly, to investigate the effects of properties of the rock and the flow rate on the results. The rock samples were naturally occurring sandstones from different locations and were similar to petroleum-bearing formations. The properties of the seven samples showing the range in porosities and permeabilities are given in Table 1. The mean pore sizes were calculated from mercury penetration data by averaging the radius with respect to pore volume. The details of this method and comparison with other procedures for estimating 7 are given elsewhere. Four fluids, nitrogen, carbon dioxide, helium and 10 weight per cent sodium-chloride solution were used with each sample. For Bartlesville sandstone, BA-5, runs were made at mean pressures from 15 to 250 psig using nitrogen. The other measurements were carried out at a mean pressure of 100 psig. The maximum temperature range eacountered was 70° to 300°F. The flow rate of fluid ranged from about 1.0 to 130 Ib/(hr)(sq ft), and this corresponded to a modified Reynolds-number range of 5 x 10-4 to 1.0. The variation in Prandtl number was 0.70 to 4.1. EXPERIMENTAL WORK The equipment consisted of apparatus to supply a constant flow of gas, or salt solution, at constant pressure to the bottom of a vertical test section, and metering and flow-regulation apparatus after the test section. The flow of salt solution was

By D. N. Dietz

A method for determining average reservoir pressure is presented, which is simpler to apply than that devised by Matthews. Brons and Hazebroek. For bounded reservoirs, identical results are obtained if stabilized-flow conditions prevail. The present method yields inferior results in the transient state. The method can, with a slight modification, also be used for water-drive reservoirs. INTRODUCTION In the method proposed by Matthews, Brons and Haze-broek' for determining average reservoir pressure in a multi-well reservoir, the cumulative production (the production time of each well) enters twice: once when the buildup is plotted against In (t + t)/At to arrive at p*, and a second time when the correction, p*-p is determined with one of the several formulas for differently shaped drainage areas. Once a steady state has been attained, however, the previous production history should be immaterial. The same pressure distribution could have been arrived at after different cumulative productions of the individual wells. In principle, therefore, it should be possible to determine average pressures without referring to cumulative productions. In the following paragraphs an expression is presented for the difference between the pressure in a producing well and the average pressure of its drainage area. Then the build-up time needed to overcome this difference is indicated. CASE OF A CIRCULAR DRAINAGE AREA AND A CENTRAL WELL PRESSURE DISTRIBUTION BEFORE SHUT-IN The general differential equation of radial flow (see Muskat, Eq. 10.2) may be written In the steady state, the rate of production of the well is equal to the rate of expansion of the fluid contained in the the drainage area; thus

Jan 1, 1966

By E. P. Fleming

COMPARED to the situation abroad, the domestic industry continues to lag both as regards the production and consumption of newly mined lead. During 1938 we produced and consumed slightly over 20 per cent of the world output, whereas ten years ago the figure was nearly double this pro- portion. Labor difficulties and absence of demand were chiefly responsible for the general inactivity. In the foreign field, in spite of low metal prices, production and consumption of lead equaled or exceeded all previous records. Practically all the large companies, with the exception of those in Spain, increased operations, though it should be noted that the foreign lead mines have higher-grade ores than domestic mines. In view of the rapid expansion of the foreign industry, it is natural to expect greater progress abroad, particularly in process metallurgy.

Jan 1, 1939

By Andrew Cosgarea, William R. Upthegrove, Morteza Mirshamsi

The capillary-reservoir technique was used with lead-210 and cadmium-115m to determine the self-diffiLsion coefficients of both cadmium and lead in the liquid binary Cd-Pb system. The self-diffusion coefficients of pure cadmium and pure lead were obtained and were compared with the theoretical predictions. Good to excellent agrement between the experimental and predicted values was obtained. The self-diffusion coefficients of cadmium were tneasuved in alloys containing 2.50, 9.13, 17.40, 31.00, 45.00, 69.00, and 97.00 lot pct Cd by determining- the amount of cadniiutn-115m which diffused out of a small-bore capillavy into an infinite reservoir during- a given time peviod. Sinzila7-measurements were made with lead-210 to determine the self-diffusion coefficients of lead in these identical alloys. Diffusivities were determined from measurenzents performed in the temperature interval of 290" to 480°C. The results were correlated with the Ar-vhenius equation, and the maximum variation of the equation parameters (Q and Do) was also inrestigated . THE theory of diffusion in liquids, particularly liquid metals, is relatively undeveloped in contrast to that for the gaseous and solid states. Although the practical application of liquid metals as heat-transfer media has become increasingly important, few liquid-metals systems have been investigated. Experimental data of fundamental significance in this field are not readily obtained, which may explain but not justify the present lack of knowledge. What work has been completed is primarily restricted to liquid diffusion of pure metals; little work has been done in liquid-metal diffusion of binary mixtures. A review of liquid-metal diffusion theory and research is available elsewhere.1-4 In an effort to add to the knowledge of liquid-metal systems and to increase the basic understanding of the diffusion process in liquids, a study of diffusion in the binary-liquid system, Cd-Pb, was undertaken. The capillary-reservoir technique5 was employed to measure the self-diffusion coefficients of cadmium and lead in molten binary alloys. Measurements were made with seven selected compositions and over a temperature range from 290° to 480°C. The experimental apparatus consisted essentially of the following items: constant-temperature bath, diffusion cells, capillaries, capillary-filling device, and a radioactive tracer counting system. EXPERIMENTAL APPARATUS Constant-Temperature Bath. A cylindrical steel vessel, 8 in. in diam and 15 in. deep, surrounded by an insulated heating coil was used with a sodium-potassium nitrate salt mixture heating medium. The bath was maintained slightly below the desired control temperature by the furnace-heating element; and a 250-w heater, actuated by a Bayley proportional temperature controller, was utilized for the final control of the temperature. A constant-speed mixer stirred the salt to insure a uniform temperature within the bath. Four calibrated Chromel-Alumel thermocouples were placed at various positions in the salt bath to verify the absence of temperature gradients. The observed temperature variation during any diffusion run was less than 0.l°C. The entire furnace assembly was mounted on four shock absorbers to exclude building vibrations and the stirrer propeller blades were adjusted so not to induce vibrations within the reservoir. A schematic diagram of the furnace and the constant-temperature bath is shown in Fig. 1. Diffusion Cell. The diffusion cells and associated parts were the same, except for slight modification, as the one used by walls1 in this laboratory, and are shown in detail elsewhere.' A graphite crucible, 4 in. long and 40 mm (1-1/2 in.) ID, enclosed in a 60-mm (2-1/4 in.) Pyrex tube cell about 18 in. long, was used as a container for the melt. The reservoir (molten alloy in the graphite crucible) was usually about 2 to 2-1/2 in. deep. Graphite was used because of its satisfactory nature as a refractory material and the low solubility of carbon in molten Cd-Pb alloy.677 The Pyrex cell was closed at the bottom and fitted at the top (open end) with a 2-in. Dresser coupling. A brass flange was welded to the top of the coupling. The upper part of the diffusion assembly was bolted to this flange with an O-ring seal. The lower part of the diffusion cell was supported in a 3-in. brass cylinder which was open to allow for circulation of salt around the cell. The top assembly consisted of two synchronous motors, a drive shaft, a thermocouple well, and controlled-atmosphere inlets and outlets. One motor was used for rotation of the capillaries at a rate of 1/2 rpm in the reservoir during the diffusion run. The other motor was used for the vertical positioning of the capillaries and the capillary holder by means of a simple screw drive. The capillary holder and drive assembly were lowered into the reservoir for the run and raised after the desired diffusion time at a rate of approximately 0.4 in. per min. Capillary holders were made of graphite. These

Jan 1, 1967

By D. C. Reynolds

Recent experiments with II-VI compounds have shown that they hazle considerable potential for laser applications over a broad region of the optical spectrum. It may be possible to cover the spectrum continuously from 3200A (ZnS) to the far infrared (CdHg:Te) since HgTe is a semimetal. At this writing laser action has been observed in ZnS, Zn0, CdS, CdSe, CdS:Se, CdTe, and some of the CdHg:Te alloys. Of particular interest are those lasers operating in the zlisible and near ultraciolet regzons of the spectrum where detectors of high sensitivity are available. The lasing transitions in II-VI compounds are bound exciton transitions some of which have been identified in auxiliary experiments. High efficiencies and low thresholds for lasing hare been achieved almost exc1usively in plutelet-type crystals. The greater crystalline quality exhibited by the phtelet-type material is shown to result from the crystal growth habit. Phonon scattering- of conduction electrons to the ground-state exciton is discussed ill relution to Lou thresholds and high efficiencies for lasing- observed in the CdS:Se solid solutions. The first successful semiconductor laser operation was achieved in the III-V compounds. It is possible to choose a material in this group that will operate between approximately 0.65 and 8.5 . There are at least two reasons why one would like to have a laser operating at shorter wavelengths. First, it would be easier to experiment with a laser operating in the visible region of the spectrum, and also more desirable to have high-in tensity visible light sources. Second, the most sensitive photomul-tiplier detectors are available in the visible and near ultraviolet regions of the spectrum. It is known that II-VI compounds are direct-band-gap semiconductors and as such offer the potential of operating at any specified wavelength between 3200 (ZnS) and 7772A (CdTe). Light emission from II-VI compounds has been the subject of numerous investigations for many years. These investigations were all primarily concerned with noncoherent emission. It has been only recently that coherent emission from these compounds has been observed. To date, laser operation has been demonstrated in CdS, CdSe, and the solid solutions of CdS:Se, ZnS, ZnO, and CdTe. These compounds cover an appreciable portion of the optical spectrum from the ultraviolet to the near infrared. In considering laser applications, the use of lasers in communication's systems offers many desirable features. In any operation of this type one must consider the losses in transmitting the radiation from the source to the detector. Atmospheric absorption in the visible and near ultraviolet is variable and greater than in certain regions of the infrared. It might be concluded that for long-range communication systems an infrared laser operating in a spectral region that is coincident with a transmission window in the atmosphere would be preferable. However, one cannot overlook the possibility of operating a system in the sensitive region of a highly sensitive photomultiplier detector or other light-amplifying system. LASER CONSIDERATIONS To produce a source of coherent radiation it is necessary to achieve a population inversion. In the case of semiconducting materials it is necessary to raise the electrons from one energy state to a higher-energy state relative to it. In semiconductors, this population inversion can be achieved by three different techniques: 1) Current Injection. This technique uses a p-n junction biased in the forward direction. Large numbers of electrons are injected from the n region into the p region, and recombination occurs close to the junction. An inverted population is obtained in this region and the recombination radiation propagates parallel to the junction. This type of pumping has been used in the GaAs junction-type lasers but has not been successfully employed in the II-VI compounds. 2) Optical Pumping. In this case, one uses photons to obtain a population inversion by exciting electrons to higher-energy states. The pump sources are flash lamps or arc lamps and, occasionally, other laser sources when such sources have the appropriate energy for exciting the electrons. The disadvantage of this type of pumping is that flash lamps put out a rather broad spectrum of radiation, whereas the laser material has a rather narrow region of absorption. This results in an inefficient process. Laser sources provide efficient pump sources but the number of usable wavelengths is limited. 3) Electron Beam Pumping. In this technique, the laser sample cavity is bombarded with electrons having energies in the range from approximately 10 to a few hundred kv. The bombarding radiation excites electrons from valence to conduction band states in the semiconductor, giving rise to an inverted population. This type of pumping has been used successfully in several 11-VI compounds.

Jan 1, 1968

By AIME AIME

THE meeting" of the Rare Minerals and Metals Committee was held Monday afternoon, Feb. 17; Donald M. Lidclell, chairman, presiding. The first paper (T. P. 279), "Progress in the Use of Tantalum," by George W. Sears, was read by Mr. Smyth. Dr. Sears' paper contains an interesting summary of the uses, alloys and ores of tantalum and a resume of present method of reduction. The uses of tantalum is based on its extreme rise to the reaction of even the strong mineral acids, its great avidity for the common gases and its capacity for transforming alternating to direct current. Tantalum, as an alloy material, has received considerable study and many alloys have been reported. Among them three types appear to .be most prominent, alloys of high melting point, hard alloys and acid rising alloys. As the estimated quantity of tantalum in the earth's crust is less than that of gold, it must be looked upon as n rare metal. Australia is the greatest producer and the Black Hills of South Dakota produce minor amounts. As the one type of mineral available contains both tantalum and columbium, the extracting and metallurgy of tantalum are difficult chemical processes. Greater simplicity in this and the development of a market for columbium would undoubtedly be of great benefit to the tantalum industry, andl make for a greater use of tantalum produced.

Jan 1, 1930

By AIME AIME

The following report is published for the information of the members: Meetings. Two meetings for the reading and discussion of papers, etc., have been held during the year 1907-namely, the Ninety-second meeting, held April 16 to 20 in New York, N. Y., and the Ninety-third meeting, held July 23 to 30 in Toronto, Canada. The proceedings of these meetings, including descriptions of the entertainments and excursions connected therewith, have already been published and distributed to the members of the Institute; the New York meeting in Bi-Monthly Bulletin, No. 15, May, 1907, pp. 541 to 559, and the Toronto meeting in Bi-Monthly Bulletin., No. 17, September, 1907, pp. 847 to 875. In addition to these " Proceedings," there were also published in Bi-Monthly Bulletin, No. 15, May, 1907, an illustrated description of the United Engineering Society building (p1 vi. to xxvi.), and a record of the exercises attending its dedication, including the addresses of Andrew Carnegie, Arthur T. Hadley, Samuel Sheldon, Frederick R. Hutton, John Hays Hammond, and T. C. Martin (pp. xxxviii. to lxv.). At the New York meeting, 43 papers and- discussions were presented, and the names of 297 members and guests were registered at the Institute headquarters., this number, however, does not represent all who were present at the sessions and excursions. At the Toronto meeting, 23 papers and discussions were presented. The number of members and guests registered at the Toronto headquarters was 191, which doubtless does not include the names of all who were present at the sessions, or took part in the numerous excursions and visits around Cobalt.

Mar 1, 1908

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680' to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,' however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated' dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski's measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving' a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski's result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski's shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur' are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955

Attention is called to the changes in officers of the Committee, whereby Albert Sauveur becomes Vice-Chairman, and Herbert M. Boylston, Secretary. Three new members of the Committee have been added, as follows : J. Esrey Johnson, Jr., William Kelly, William R. Walker. The death of Dr. F. WV. C. Schniewind is a severe personal blow to the members of the Committee, as well as a loss on the technical side that will be hard to fill. During the absence of Mr. Kirchhoff in Europe the activities of the Committee will be under the charge of Professor Sauveur.

Jan 4, 1913

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969