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By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By William E. Harris

Time and experience have demonstrated that by means of the Waelz process zinc, lead, cadmium, arsenic, antimony, bismuth and tin can be volatilized satisfactorily. In this way difficult gold ores are being treated to allow for the recovery of the precious metal. Iron ore containing zinc is being treated to remove the zinc and recover the iron. In Germany, thallium is being recovered in commercial quantities from the zinc oxide fume; indium, germanium and gallium are also concentrated to a degree warranting recovery, even though these rare metals are only recognizable in the ore by means of the spectroscope. The physical, chemical or mineralogical condition of the raw material affects very little the applicability of the process. The name Waelz is derived from the German word Waelzen, meaning a "trundling motion," which very aptly describes the movement of the charge through the slowly rotating kiln. The recovery of zinc and lead by volatilization in a rotary kiln has its origin in a process patented in 1910 by Edward Dedolph, of British Columbia. The Dedolph patent was taken over by the Metallgesell-schaft of Frankfurt-on-Main, Germany, which in cooperation with the Griesheim-Elektron, now a part of a large industrial combine, introduced certain improvements (Ohlmer, Specketer patents), but without bringing the process to a state suitable for large-scale operations. The war temporarily stopped all work on the process, and it was not until after the war that the Krupp Grusonwerk, of Magdeburg-Buckau, Germany, quite independently of the Metallgesellschaft, instituted research work in this field of metallurgy, which in 1923 led to the Waelz process proper. The Krupp Grusonwerk and the Metallgesellschaft A.G. later on collaborated, and by their joint efforts further developed and perfected the Waelz process, which they are marketing together as "Waelz-Gemeinschaft." The process is capable of treating a varied type of material; for instance, oxidized and sulphide zinc ores, calamine (zinc carbonate ore) waste dumps, jig tailings, jig slimes, table concentrate slimes, brass ashes, zinc-bearing iron ores (where the iron sinter is the real objective and the zinc oxide a by-product), electrolytic-zinc leach residues, zinc muffle residues and works sweepings, lead-furnace slags, tin ores and slags, anti-

Jan 1, 1937

By A. Jowett

An attempt is made to explain differences in the size-by-size response to flotation of some sulphide minerals. Physical factors involved in particle-bubble collision and adhesion, and also in possible subsequent disruption of aggregates, are considered especially in relation to flotation of the coarser sizes. Emphasis is on practical observations and their significance, with an essentially qualitative theoretical treatment designed to form hypotheses for further experiments. In particular, the theoretical effects of contact angle and induction time are examined. An argument is developed which suggests a rapid increase in induction time as particle size increases, except for particles small enough to be moving under laminar flow conditions. This can adequately explain poor recoveries of coarse particles in flotation without a need to assume disruption of particle-bubble aggregates in turbulent zones in a flotation cell. Flotation recovery is shown to be very sensitive to small changes in induction time. Consideration of the physics of disruption of particle-bubble aggregates leads to the conclusion that this mechanism does not adequately explain differences in flotation recovery of coarser sizes of some sulphide minerals. For example, to explain differences in recovery of coarse galena and chalcopyrite by this mechanism would necessitate accepting that conditioning with ethyl xanthate which would promote a 60º contact angle at a galena surface would promote only an 11º angle at a chalcopyrite surface. Small differences in induction time arising from differences in surface chemical characteristics of the various minerals offer a more satisfactory explanation of differences in recovery of coarser sizes.

Jan 1, 1980

By Raymond B. Ladoo

The Paley report made little attempt to project future production and consumption for any industrial mineral except fluorspar and only about a dozen minerals were mentioned by name. Except for fluorspar the treatment consisted mainly of statistics of production, consumption, imports, and sometimes reserves up to 1950. FLUORSPAR In 1954 the author had occasion to evaluate the Paley fluorspar estimates. At that time a fairly detailed study of the world picture was made and bases for the Paley estimates were studied. Data for later years confirm, in the main, the conclusions reached in this earlier report and it will be drawn upon here.

Jan 11, 1959

By R. H. Maes, R. E. de Strycker, J. J. Jacobs

A simple method, based upow density measurements, has been perfected in order to determine the critical temperature of liquid miscibility gaps. Applied to the Pb-Cu system, it yielded a value of 980"C for the critical tempevature of the miscibility gap in this system. In the Pb-Cu-As system, the immiscibility between lead and coppev evolves towards a miscibility gap be-tween lead and copper arsenides; the liquation temperatures were determined joy different avsenic contents and values up to 1065°C were found. Combining these results with those given by the clzemical analysis of liquid samples taken at dqj.event temperatures, it has been possible to make a cowzplete determination of the liquid miscibility gap in this ternary system. In the Pb-Cu-Fe-As system, a ternary miscibility gap has been discovered; for some compositions, the molten and slowly cooled alloys separated into three layers: an Fe-As alloy, a Cu-As alloy, and a lead-rich layer. ThE Pb-Cu-Fe-As system is of interest for the study of the behavior of speiss or arsenical alloys in the lead blast furnace. The speisses produced in lead metallurgy generally have complex compositions, but they may be considered, in a simplified way, as a mixture of copper, iron, nickel, and cobalt arsenides; there is often an excess of metallic constituants, and lead is also present. Speisses liquate from lead at various temperatures according to their composition; according to industrial experience, iron speisses are already distinctly separated from lead bullion at temperatures of the order of 1100°C, whereas copper speisses only begin to liquate from lead at much lower temperatures, near their solidification points, which were never accurately determined until now. Besides these considerations of practical interest, the present study is of importance for the knowledge of liquid miscibility gaps. Particularly the data of the literature about critical temperatures of liquation are incomplete and present sometimes considerable disparities; a method has been perfected in the present work to determine these temperatures with accuracy. MISCIBILITY GAP OF THE LEAD-COPPER SYSTEM Review of Literature. The generally admitted outline of the Pb-Cu equilibrium diagram is shown by Fig. 1. This figure, with its numerical indications, is taken from the review of Hansen and ~nderko;' compositions are given in weight percent, as will be the case in the remainder of this paper. Between 36 and 87 pct Pb, Pb-Cu alloys separate into two layers, in the liquid state. The critical temperature of liquation has been much disputed in earlier studies, where values up to 1500°C were claimed; but a reliable study of ~ohnen,' based upon differential thermal analysis, gave a value of 990°C; this rather low value was verified by a recent study of Schiirmann and Kaune? based upon thermodynamical properties of the Pb-Cu alloys, which predicted a value of 1002°C. Liquid miscibility gaps were also studied by means of chemical analyses. Satisfactory results were generally obtained with the method consisting in taking samples of the two liquid layers in equilibrium and submitting them to chemical analysis; however, this method becomes delicate near the critical temperature. With this technique, Friedrich and waehlerts ob-

Jan 1, 1968

By C. Upthegrove

DURING the past year considerable work dealing with physical properties of cartridge brass was done at the University of Michigan in cooperation with the Ordnance Department of the U. S. Army. This paper gives some of the data bearing on the effect of the anneal, previous to the final reduction or rolling, on the physical properties, particularly the hardness. Various phases of the subject of physical properties of cartridge brass have been presented by different investigators. Mathewson and Phillips1 refer to the work of Grard, in 1909, as the first systematic presentation of the relation between temperature-and time of anneal; changing of physical properties and microstructure, and the previous reduction by cold rolling. They discuss the relation between time and temperature of anneal and the previous reduction by cold rolling also; the relation between physical properties and grain size of annealed brass. The degree of deformation previous to the annealing was found to determine the temperature at which recrystallization and corresponding changes in physical properties would take place. Bassett and Davis,2 in establishing the relation between grain size and Brinell hardness; found the hardness for low-temperature annealing to be dependent on the previous degree of reduction, while for anneals above a certain temperature the hardness after the anneal was independent of the degree of reduction. Actual differences in hardness, due to the degree of reduction, disappear only on annealing at 600° C. or above; though the differences for metal subjected to different degrees of reduction and annealed at temperatures between 350° and 600° C. were found to be relatively small. In their determination of the relationship of grain size to Brinell hardness, Bassett

Jan 5, 1922

By W. R. Strickler, P. Hazebroek, M. Prats

The pressure and production behavior of a homogeneous cylindrical reservoir producing a single fluid through a centrally located vertical fracture of limited lateral extent was determined by using mathematical methods to solve the appropriate differential equation. It is assumed that there is no pressure drop within the fracture — that is, that the fracture capacity is infinite. It was found that the production-rate decline of such a reservoir is constant (except for very early times) when the flowing bottom-hole pressure remains constant. The production-rate decline increases as the fracture length increases. Thus, the lateral extent of fractures can be determined from the production-rate declines before and after fracturing or from the decline rate after fracturing when the properties of the formation and fluids are known. The production behavior over most of the productive life of such a fractured reservoir can be represented by an equivalent radial-flow reservoir of equal volume. The effective well radius of this equivalent reservoir is equal to one-fourth the total fracture length (within 7 per cent); the outer radius of this equivalent reservoir is very nearly equal (within 3.5 per cent) to that of the drainage radius of the fractured well. The effective well radius of a reservoir producing at semisteady state is also very nearly equal to one-fourth the total fracture length. It thus appears that the behavior of vertically fractured reservoirs can be interpreted in terms of simple radial-flow reservoirs of large wellbore. INTRODUCTION An earlier report1 has considered the effect of a vertical fracture on a reservoir producing an incompressible fluid. That investigation of the fractured reservoir producing an incompressible fluid was started because of its simplicity. Thus, pertinent behavior of fractured reservoirs was obtained at an early date, while experience was being gained of value in the solution of more complicated fracture problems. One of these more complicated problems, and the one discussed in this report, considers the effect of a compressible fluid (instead of incompressible fluids) on the production behavior of a fractured reservoir. In the incompressible-fluid work mentioned, it was shown that the production rate after fracturing could be described exactly by an effective well radius equal to one-fourth the fracture length whenever the pressure drop in the fracture was negligible. Because of the simplification in interpretation, it is a matter of much interest to determine whether the production behavior of reservoirs producing a compressible liquid could be described in terms of an effective well radius which remains essentially constant over the producing life of the field. The details of the mathematical investigation are given in the Appendixes. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The reservoir has an impermeable circular cylindrical outer boundary of radius re. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below the producing layer (reservoir). It is assumed that there is no pressure drop in the fracture due to fluid flow. Fig. 1 indicates the general three-dimensional geometry of the fractured reservoir just described. When gravity effects are neglected, the flow behavior in the reservoir is independent of the vertical position in the oil sand. Thus, the flow behavior in the fractured reservoir is described by the two-dimensional flow behavior in a horizontal cross-section of the reservoir, such as the one shown in Fig. 2. Production is due to the expan-

By G. S. Cole

The temperature has been measured ahead of stationary solid-liquid interfaces under conditions approximating luzidirectional heat flow and therefore unidirectional solidification. Natural convection flow patterns may be deduced from the temperature distributions , temperature fluctuations, and shape of the interface. Fluid flow increases with the height and the rate of heat transfev through the interface and this is further manifested by a deviation of the interface from aflat vertical plane. The influence of fluid flow on solute inhomogeneity during alloy crystal growth can be inferred from the observed temperature distributions. A buoyancy force exists in the liquid ahead of a vertical solid-liquid interface, caused by a difference in density between cold fluid near the interface and warmer fluid in the bulk liquid. When the viscous and inertia forces in the melt exceed this buoyancy force, a flow of fluid takes place, termed natural or free thermal convection. Natural convection in purely liquid systems has been extensively studied for many years. 1"u On the other hand, fluid flow during horizontal crystal growth has oniy recently been the subject of experimental investigation."-25 The requirements for horizontal crystal growth differ from other heat flow systems. The small aspect ratio (ratio of height of cold wall to length of fluid) has never been considered. The uniform furnace gradient which supplies heat radially (and not necessarily symmetrically) differs from previous boundary conditions of uniform heat flux at the cold and hot ends. And most important of all an isothermal s/l interface is present which can adjust its shape and position to conform to heat and fluid flow. All of these boundary conditions involve complexities which cannot be readily solved analytically. Preliminary observation has demonstrated the penera1 shape of the natural convective flow pattern in transparent media.20'24'25 The flow is circulatory, directed toward the interface at the surface of the liquid, down and away from the interface at the bottom, and then up at the hot end of the melt. During crystal growth such a flow may interact with the solute boundary layer at the s/l interface to affect solute incorporation.M'1B|28'i!T Evidence has also been presented recently to show that thermal convective flow will affect the structure of ca~tin~s.~~-~~ The rate of heat transfer (conduction plus convection) in a given fluid system is a function of the temperature difference between the hot end of the liquid and the s/l interface and the height of the interface. At the lowest values of these variables* all heat is *It has been shown' that adverse temperature gradients as low as O.OOS°C oer cm are sufficient to cause convection. transferred by conduction. When the temperature difference or interface height are increased, laminar fluid flow commences and heat transport takes place by laminar convection as well as by conduction; turbulent heat transfer takes place at higher values of these variables. In the transition region between laminar and turbulent flow, boundary layer separation takes place; fluctuations in temperature are also noted and increase in amplitude and frequency as turbulence becomes dominant. In this paper, fluid flow patterns in the melt ahead of a stationary interface are deduced from observations of temperature distribution and fluctuations, heat flow rate, and interface shape. The fluid flow ahead of advancing interfaces and the effect of such flow on solute incorporation may be inferred from these measurements on stationary interfaces. Observations during enforced fluid motion will also be considered. EXPERIMENTAL PROCEDURE The metal was contained in a lava boat 10 cm in length, 1+ cm in width, and 2 cm in height, as shown in Fig. 1. A water-cooled, molybdenum block heat-sink is at one end of the boat; surrounding this assembly is a slotted stainless-steel tube noninductively wound with a nichrome heating element. Temperature was measured by 38-gage Chrome1 vs Alumel thermocouples sheathed in 0.05-cm-diam graphite-coated stainless-steel tubing, which were moved longitudinally and vertically through the melt by means of a two-dimensional motorized micrometer stage. In some experiments the thermocouple junction was exposed, but in the majority of experiments the junction was welded to the sheath tip; no significant difference

Jan 1, 1968

By William A. Kennedy, Jonathan R. Stahl

This paper deals with the phenomenon of water held in a leach dump due to capillarity. Water is shown to be retained in the fine pores of the ore as well as in the interstices between the rock and soil particles. Upon drainage, Chino leach dump material shows two distinct capillary systems and a double capillary curve is often obtained. Both the igneous and the sedimentary rocks composing the leach material are shown to have appreciable porosity but little permeability. Fluid flow is, therefore, restricted to the interstices between the rock and soil particles. The irreducible water saturation for the aggregate is found to be 884 for the -48 mesh material and 235 for the448 mesh to one inch material. The composite sample of minus one inch dump material had an irreducible water saturation of 52 percent. The irreducible water saturation in the fine pores of the ore was found to be between 73 and 76 percent. Very coarse pores or channels between large rocks exhibit essentially zero capillary retained water. The presence of fine material in a dump can cause high water saturations to be retained and these saturations may be mistaken for perched water tables. Perched water tables can be drained but capillary water will be retained. Capillary pressure data can aid in distinguishing between perched water tables and capillary retained water.

Jan 1, 1974

By R. G. Knickerbocker, W. E. Brown, G. J. Vahrenkamp, M. M. Fine

THE results of a research and development laboratory and pilot-plant mineral-dressing investigation by the Bureau of Mines of the complex copper-lead-cobalt-nickel ores of southeast Missouri are reported in this paper. This investigation, in cooperation with the National Lead Co., showed that separate concentrates of lead, copper, and cobalt-nickel could be made by fine grinding and flotation. An industrial plant built subsequently by the St. Louis Smelting and Refining Div. near Fredericktown, Madison County, Mo., produced such concentrates during the war years. Present commercial production at the mill is limited to lead and copper concentrates, but research to permit economic utilization of the cobalt and nickel values is continuing. The complex sulphide deposits near Frederick-town in Madison County, Mo., have an operating history that dates back to the years preceding the Civil War. Perhaps these operations can best be summarized in terms of output which are given by Tyler: "Previous to 1900, the Mine la Motte Co. shipped cobalt ore to Swansea and in 1903 produced 120,000 pounds of oxide in a Missouri plant. Another cobalt refinery erected in 1906 by the North America Lead Co. at Fredericktown, Mo., operated intermittently until 1910. In 1909 it produced 83,384 pounds of cobalt oxide, 328,403 pounds of nickel, 8,314 tons of nickel-cobalt concentrates, 600 tons of copper concentrates, and 1,353 tons of lead concentrates. This plant was purchased at a forced sale in 1915 by the Missouri Cobalt Co., which produced a certain amount of oxide in 1918 and in 1920 recovered 102,410 pounds of cobalt oxide and cobalt hydrate, valued at $262,810." According to Buehler,2 "The ore, which consists of a complex mixture of the sulphides of cobalt, nickel, copper, lead, and iron, occurs at the contact of the pre-Cambrian porphyry and the overlying Lamotte sandstone and Bonneterre dolomite." The source of most of the cobalt and nickel is siegenite, a member of the linnaetite series of minerals. Its composition is variable, and although the chemical formula may be given as (CoNi),S,, it usually contains both iron and copper. The siegenite is characterized in this instance by an intimate association with chalcopyrite, and to a lesser extent with iron sulphides. Galena, on the other hand, while dis- seminated throughout the ore, is not closely bound to other constituents. Gangue is composed essentially of dolomite and quartz. Petrographic examination showed that fair liberation of sulphides and gangue could be attained at — 100 mesh. Complete liberation of micronsize inclusions, particularly of sulphides in each other would not have been possible at —400 mesh. Beneficiation Studies Many samples of the southeast Missouri ore were tested, but most of the work was confined to five samples of churn drill cuttings weighing 15 tons. The samples were reportedly representative of five sections of the deposit and were tested individually and as a composite. Only the results of the tests on the composite, which contained 1.28 pct lead, 2.03 pct copper, 1.06 pct nickel, 0.87 pct cobalt, 3.57 pct iron, 15.4 pct lime, and 23.9 pct silica, are presented in this report. In view of the rather complex and intimate association in the mineralogical composition of the ore, flotation was the logical choice in the selection of a beneficiation process. Other mineral dressing unit operations were considered as an adjunct to flotation, but none were beneficial. Many tests were made on these samples to determine the flotation characteristics of the mineral siegenite. As a result of this work, it was noted the siegenite was intermediate in floatability between chalcopyrite and galena on one extreme and iron sulphides on the other. The difference in floatability between siegenite and the iron sulphides was not very great and, in general, the same reagents that depressed pyrite and marcasite would also, in slightly larger quantities, depress siegenite. This tendency for siegenite

Jan 1, 1952

By Paul L. Russell

Of the potential applications of nuclear explosives to mining, excavation is perhaps the most obvious and the best understood, and probably the most practical for use in the near future. Large quantities of rock and earth can be moved by proper emplacement of nuclear explosives, but economic and practical relationship must be determined between the known capabilities of nuclear explosives and the required excavating to remove overburden. On an energy yield basis, even the cheapest of the present commercial explosives cost more than the most expensive nuclear explosive. Comparing the energy yield of a megaton thermonuclear device with the yield of TNT shows that one energy yield per dollar is 400 times greater for the thermonuclear device. However, small-yield nuclear devices (a few 10's of kilotons yield) are less efficient blasting materials than chemical explosives, with the result that the heat of explosion is utilized less effectively. While only 1 lb of conventional explosive is required to excavate 1 cu yd of rock, or about 2 million cu yd per kiloton, nuclear devices excavate from 100,000 to 300,000 cu yd per kiloton. This changes the economic situation, and it is thus apparent that nuclear explosives are cheaper only for the large explosions.

Jan 6, 1964

By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953

By R. P. Brown

To gain some idea of the progress recently made in the measurement of high temperatures, we must review the temperature-measuring devices of the past. As far back as 1782, Wedgewood, a famous potter in England, attempted to measure his, kiln temperatures by means of clay trials, or test pieces, that indicated the expansion or contraction that occurred with certain changes in temperature. He also produced cones off clay, formed of various mixes, to form a whole series for the range of temperature met with, in firing clay products. These cones are still extensively used to measure kiln temperatures in the pottery industry. Cones are affected not only by time but by temperature and the rate, of firing, consequently, they are not an accurate measure of temperature. In addition it has been common practice for years to attempt to measure temperatures with fusible salts. Capsules of these are inserted in the furnace and indicate, by melting; when a certain temperature, has been attained. While' such salts cannot be considered a precision form of temperature-measuring device, they have proved reasonably accurate in checking temperature.

Jan 9, 1919

By L. Segle, R. Resnick

NUMEROUS experiments in the past few years have proven that void formation occurs quite generally in the diffusion zone of bimetal specimens1-4 The phenomenon has been explained in terms of the accumulation of lattice vacancies resulting from unequal diffusion of the constituents and their eventual precipitation as holes.= Attention has recently been directed to the fact that voids also form within homogeneous metals during high-temperature creep.' The idea has been put forward that these voids form by the condensation of excess lattice vacancies generated by intersecting dislocations.".' If the precipitation of lattice vacancies from solution is treated as a nucleation and growth process, the predicted vacancy concentration for homogeneous nucleation of voids at an observable rate is 100 to 1000 times the normal thermal equilibrium concentration. It appears that voids actually form during diffusion at vacancy supersaturations which are much lower than this8 According to the calculations of Machlin,' the same must be true for voids formed in homogeneous metals during creep, if these are considered to arise from the precipitation of lattice vacancies. Therefore, if the vacancy mechanism is valid, it seems that the holes which form in diffusion and creep specimens are heterogeneously nucleated by imperfections or impurities in the metal. Irregularities in the frequency and distribution of voids in diffusion couples bear out this explanation.' , It is not known at the present time what the nuclei are on which vacancies condense. Various investigators have speculated that they could be certain dislocation configurations, already existing voids produced during solidification or working, gas pockets, or inclusions in the metal. Relatedly, the precise value of the degree of vacancy supersatura-tion for void nucleation is still uncertain. An initial attempt to estimate this value from diffusion data, made by Balluffi, indicated that voids form in diffusion couples at vacancy concentrations which may

Jan 1, 1958

By A. N. Holden

A DISLOCATION mechanism has been described by Cottrell' by which metals can yield locally, I. form Liiders bands, giving rise to a characteristic stress-strain curve with a sharp yield point and appreciable strain at constant or decreasing stress. It is undoubtedly the best mechanism that has been suggested to date." In its present development, however, the dislocation mechanism provides a more satisfying explanation for the sharp yield point than for the extensive localized flow occurring at the lower yield stress. The primary objective in this paper is to extend the dislocation mechanism to account for localized cataclysmic flow by a dislocation collision process and to give experimental evidence to support such a process. Only the yielding of iron containing carbon -will be discussed, although other metal-solute systems are known to behave similarly. Cottrell Mechanism In brief, Cottrell explains the yield point in the following way: The dislocations in iron which must propagate to produce slip usually lie at the center of local concentrations of carbon atoms, since segregation about these dislocatlons relieves some of the local stress resulting from them. A dislocation surrounded by a "cloud" of carbon atoms is thus anchored, and a higher stress is required to set it in motion than to move a free dislocation. Considering all available dislocatlons to be anchored in this fashion, the iron exhibits a yield point when the first dialocations break free and move through the lattice causing slip. This first breaking away of a dislocation enables other dislocations to break loose by "interaction" and the process becomes a cataclysm producing local deformation or Luders bands. The yield point in the stress-strain diagram for iron is absent in freshly deformed material, but returns gradually with time; the phenomenon is one aspect of what is called strain aging. The rate at which the yield point returns following straining depends on the temperature of aging. According to Cottrell the rate of return of the yield point in strained iron is limited by the rate of diffusion of carbon at the aging temperature, the mechanism is onr: of reforming the solute atmospheres around carbon-free dislocations that had stopped moving coincident with the removal of stress. If the specimen is retested immediately after straining and unloading, carbon will not have had time to diffuse to, and re-anchor, dislocations and the yield point will not occur. The carbon diffusion limitation for the rate of strain aging apparently applies if the criterion for strain aging is either the change in hardness" or the change in electrical resistance" of the strained speci- men with aging time. The possibility exists, however, that the yield point actually returns to strained iron at some rate other than that deduced from hardness or electrical resistance data. Therefore, as a preliminary experiment, the rate of yield point return in a rimmed sheet steel strained 6 pct in tension was measured at 27°, 77°, and 100°C. A plot of yield-point elongation for each of these temperatures against aging time appears in Fig. 1. The aging process is described by curves which rise to a plateau value of elongation that seems independent of temperature, but at a rate that depends on temperature. Very long times lead to a further rise in the yield-point elongation above the plateau value. However, if the later increase in yield-point elongation is ignored and the log of the time to reach half the plateau value of elongation is plotted against 1/T, a straight line results for which an activation energy of about 25 kcal pel- mol may be assigned. Within the accuracy of this sort of experiment this is approximately the activation energy for the diffusion of carbon in iron (20 kcal per mol), and the carbon diffusion limitation suggested for the yield-point return on strain aging is valid. The Cottrell mechanism thus explains in a qualitative manner the occurrence of a yield point in iron and its return with strain aging. It fails, however, to explain some of the other experimental observations that have been made of the yielding behavior of iron. For example, it is known that the yield point in iron becomes less pronounced with increasing grain size. Annealed single crystals of iron have very small yield-point elongations .if indeed they have any,' compared to a polycrystalline steel. If the only requirement for a yield point is that the dislocations in the lattice of the annealed. material be anchored by carbon atoms, the difference in the behavior of single crystals and polycrystals is not explained. That a dislocation mechanism may be entirely consistent with little or no yield point in an annealed single crystal will become apparent later when dislocation interaction is discussed. Strain aging produces a definite yield point even in single crystals. This accentuation of the yield-point phenomenon in single crystals after strain

Jan 1, 1953

By Martin A. Mayers

It has long been recognized that it would be highly desirable to be able to predict the temperatures at various points in a burning fuel bed and their variations with changes of the properties of the fuel and the rate of air supply. Experimenta1 investigations of fuel-bed temperature1-4 have not been lacking, but the absence of any theoretical background has made it impossible to use the results of these tests as a basis for prediction, except in a very general may. A mathematical analysis", based on a somewhat simplified theory of the distribution of lieat in a fuel bed, lias recently been completed by the author. Even though numerical values of some of the coefficients are not known, the calculations result in some conclusions of general significance. Thus, for example, it appears that when the temperatures throughout the fuel bed can be calculated, the rate at which ignition of the fuel by underfeed action can be maintained can also be calcu1ated. The uncertainty concerning the values of the coefficients referred to above is serious limitation on the use of that method. The following paper presents a discussion of these coefficients and includes estimates of their values based on the data now available. A brief description of the theory on which the analysis is based, and some results of the calculations showing their degree of agreement with experimental results, are presented by way of introduction to the discussion of the coefficients. For a more. extended discussion of the theory, see the A.S.M.E. paper5. Theory and Comparison with Experiment The theoretical analysis is similar to that used in the calculation of the stationary temperatures in a conducting solid in the classical theory of heat concluction. The fuel bed is pictured as a uniform, continuous, porous solid through the interstices of which air can be blown and ill which combustion can take place. The solid lias a finite thermal conductivity, so that heat may be transported in any direction, against the flow of air as well as in the same direction. While it is true that nothing

Jan 1, 1938

By Martin A. Mayers

It has long been recognized that it would be highly desirable to be able to predict the temperatures at various points in a burning fuel bed and their variations with changes of the properties of the fuel and the rate of air supply. Experimenta1 investigations of fuel-bed temperature1-4 have not been lacking, but the absence of any theoretical background has made it impossible to use the results of these tests as a basis for prediction, except in a very general may. A mathematical analysis", based on a somewhat simplified theory of the distribution of lieat in a fuel bed, lias recently been completed by the author. Even though numerical values of some of the coefficients are not known, the calculations result in some conclusions of general significance. Thus, for example, it appears that when the temperatures throughout the fuel bed can be calculated, the rate at which ignition of the fuel by underfeed action can be maintained can also be calcu1ated. The uncertainty concerning the values of the coefficients referred to above is serious limitation on the use of that method. The following paper presents a discussion of these coefficients and includes estimates of their values based on the data now available. A brief description of the theory on which the analysis is based, and some results of the calculations showing their degree of agreement with experimental results, are presented by way of introduction to the discussion of the coefficients. For a more. extended discussion of the theory, see the A.S.M.E. paper5. Theory and Comparison with Experiment The theoretical analysis is similar to that used in the calculation of the stationary temperatures in a conducting solid in the classical theory of heat concluction. The fuel bed is pictured as a uniform, continuous, porous solid through the interstices of which air can be blown and ill which combustion can take place. The solid lias a finite thermal conductivity, so that heat may be transported in any direction, against the flow of air as well as in the same direction. While it is true that nothing

Jan 1, 1938

By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944