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By John H. Hollomon

In a recent paper,' a very early suggestion by Ludwik2 concerning the nature of the mechanical behavior of metals has becn reexamined and extended. In essence it was suggested that there exists, at least under certain conditions, a mechanical equation of state; that the stress required for flow depends upon the instantaneous values of the strain, strain rate, and temperature, and not upon their past values. It is proposed that under these circumstances thc stress does not depend upon past history of these variables, but is like the temperature of a gas that depends only upon the instantaneous values of the pressure and volume. This notion has not been applied to present-day studies of metals, though it is especially applicable to the study of creep. It is the purpose of this paper to analyze the significance and possible range of applicability of this idea and to determine how it influences the accepted ideas concerning creep. Stress-strain Relations It is wcll known that the stress-strain curves of metals are influenced by both train rate and temperature. For a fixed strain rate and temperature there is associated with each metal a stress-strain curve. If either the strain rate or temperature is changed a new stress-strain curve will be characteristic (Fig. I). A much more genera1 relation between the effects of these variables is possible, however. Consider the stress-strain curves of Fig. I determined at

Jan 1, 1947

By John H. Hollomon

In a recent paper,' a very early suggestion by Ludwik2 concerning the nature of the mechanical behavior of metals has becn reexamined and extended. In essence it was suggested that there exists, at least under certain conditions, a mechanical equation of state; that the stress required for flow depends upon the instantaneous values of the strain, strain rate, and temperature, and not upon their past values. It is proposed that under these circumstances thc stress does not depend upon past history of these variables, but is like the temperature of a gas that depends only upon the instantaneous values of the pressure and volume. This notion has not been applied to present-day studies of metals, though it is especially applicable to the study of creep. It is the purpose of this paper to analyze the significance and possible range of applicability of this idea and to determine how it influences the accepted ideas concerning creep. Stress-strain Relations It is wcll known that the stress-strain curves of metals are influenced by both train rate and temperature. For a fixed strain rate and temperature there is associated with each metal a stress-strain curve. If either the strain rate or temperature is changed a new stress-strain curve will be characteristic (Fig. I). A much more genera1 relation between the effects of these variables is possible, however. Consider the stress-strain curves of Fig. I determined at

Jan 1, 1947

By L. R. Jackson

It is convenient to have a consistent system of notation that will allow the representation of the entire range of complex stresses from hydrostatic compression to hydrostatic tension on plastic flow in a single diagram. Such a system is provided by making use of the fact that any complex stress system can be resolved into a hydrostatic tension or compression and a pure shear. Consider a stress system having the principal stresses This system can be resolved into a new system consisting of the three components and three pure shears. If Sm is positive, the net stress effect is hydrostatic tension; if it is negative, the effect is hydrostatic compression. In order to produce a systematic notation, a quantity that will be referred to as the "triaxial ratio" will be defined by the equation _ Sm Tr = Sm - Sm is given by Eq. I and Sl is the absolute magnitude of the largest principal stress without regard to sign. Table I lists the triaxial ratios for various common systems. Table i.—Triaxid Ratios for Various CommonSyslems Triaxial Ratio Stress System Tr Hydrostatic compression — SI - —St - -S³............................... -1 Torsion or shear -SI - S². S² = O..... O Simple tension SI. SI = SI = 0......... +0.33 Biaxial tension SI = S² S³ - 0......... +0.66 Hydrostatic tension +SI - +S³ = +S³. +1.00 Representation of Strains Strains will be plotted as "true" strains according to the system proposed by Ludwik.1

Jan 1, 1945

By E. T. Turkdogan

In this theoretical paper, a transport-reaction mechanism is suggested for the enhancement of the rate of vaporization of metals, or other materials, brought about by the process of convection and condensation. Based on theoretical reasoning it is predicted that, when there is a temperature gradient surrounding the heated object, a slight increase in the rate of vaporization brought about by natural convection is enhanced further as a result of condensation of the vapor close to the surface of the object. In order to derive the effective vapor-concentration profile, consideration is given to the super saturation of the vapor necessary for the homogeneous nucleation of the condensed phase from the vapor. For the formulation of the rate equation based on this mechanism, adequate information should be available on the transport properties of gases and vapors at elevated temperatures and the method of calculating nucleation pressures of the vapor. The methods of deriving such data are discussed in the paper and a rate equation is calculated for the vaporization of iron in helium for various temperature gradients in the boundary layer. Considerations are also given to the effect of oxygen on rates of vaporization of metals under isother ma1 and nonisotherma1 conditions. THE study of the methods of enhancement or retardation of basically transport-controlled vaporization reactions is of theoretical interest with possible practical implications. There are several ways of bringing about such effects. For example, Turk-dogan, Grieveson, and Darken1 demonstrated that the rates of vaporization of metals under isothermal conditions were increased by several orders of magnitude, up to the maximum rate attainable in vacuo, by introducing some reacting gas into the inert atmosphere surrounding the metal. Such an effect is brought about by the interaction of the counter-diffusing reacting gas and metal vapor in close proximity of the metal-gas interface. Another case which is often experienced in practice is that of vaporization affected by natural convection. Although several theoretical and experimental studies of this problem have already been made, no detailed consideration has been given to the possible effects of condensation of the vapor in the boundary layer on vaporization rates, which constitutes the subject matter of this paper. BASIC CONCEPT OF ENHANCED DIFFUSION-LIMITED VAPORIZATION When a heated object, for example a metal sphere, is submerged in a fluid medium, heat is transferred from the surface of the object to its surroundings by four simultaneously occurring transfer processes: i) free-molecular conduction at the gas-solid interface over the distance equal to the mean free path of the gas, ii) conduction and convection through the fluid-dynamic boundary layer, iii) latent heat of mass transferred, and it!) radiation. The free-molecular conduction becomes pronounced only when the total pressure in the system is very low, e.g., below 1 mm Hg. Therefore, this term may be neglected for ordinary pressures. At low mass-transfer rates, due to vaporization of the object, the contribution of process iii) to the heat transfer can also be neglected. Finally, since the temperature profile is not affected by radiation, the latter need not be considered. The natural convection is brought about by gravitational body forces arising from a decrease in the

Jan 1, 1964

By D. J. Carney, J. Chipman, N. J. Grant

An absolute calibration has been achieved for sampling and analyzing liquid steel for hydrogen based on Sieverts' values of hydrogen solubility in iron. Further checks were made in nickel, iron-nickel, and 18-8 stainless melts. The sampling method was successfully applied to a large number of commercial steel melts in various types of furnaces. The concurrent problem of sample storage was also solved. THE problem of sampling of liquid steel for hydrogen is more difficult than the problem of analysis. Hydrogen has a greater mobility than any other element; it is the only element that will diffuse out of steel at room temperature. In accordance with the known relation between temperature and diffusivity, the diffusion of hydrogen is extremely rapid at the temperature of liquid steel. Consequently, in the past, attempts to quench molten steel to retain the dissolved hydrogen have not been as successful as similar attempts with nitrogen or oxygen. The retention of hydrogen is especially difficult since it will continue to escape at room temperature even if the molten metal has been rapidly quenched. The hydrogen sampling methods may be classified broadly as (1) the rapid quenching techniques which attempt to preserve super saturation and (2) those methods which attempt to collect the gases evolved as the metal freezes and cools to room temperature. With all methods of sampling but especially with the rapid quenching methods, there is also a concurrent problem of storing the sample until analysis is undertaken. The two problems are interrelated and must be considered together when discussing liquid steel sampling techniques. The major obstacle in liquid steel sampling has been that there was no way of evaluating properly the various sampling and storage techniques which have been developed. It has not been possible to compare the accuracy of the various methods. For evaluation of sampling methods some known standard is required; this may be found in the published work on the equilibrium solubility of hydrogen in liquid iron which has been determined in three separate investigations.1,2,3 The data are shown in table I. Sieverts' original method of obtaining gas solubilities involved measurement of the volume of gas required to saturate the liquid metal contained in an evacuated bulb of known volume. This procedure, improved by introduction of high frequency induction heating, has yielded reproducible results which appear to be entirely dependable. Using Sieverts' method, it has been proved for iron and other metals and alloys that the hydrogen solubility is proportional to the square root of the pressure of the hydrogen gas above the liquid, so that one may work with various partial pressures of hydrogen to put different amounts of hydrogen in solution. From Sieverts' law it is possible to know accurately what amount of hydrogen is dissolved in the liquid metal at the time of sampling. The accuracy of a sampling method may be gauged by reference to this known solubility. It was the purpose of this investigation to develop a method for sampling liquid steel and for storing the sample so that the analytical result would represent the actual hydrogen content of the metal bath. For this purpose an induction furnace was

Jan 1, 1951

By James A. Crookston, William D. Fitzpatrick

Committee C-8 of the American Society for Testing and Materials defines refractories as "material, usually nonmetallic, used to withstand high temperature," and it defines the term refractoriness thus, "in refractories, the capability of maintaining the desired degree of chemical and physical identity at high temperatures and in the environment and conditions of use.” The ability to withstand high temperatures is critical to classifying a material as a refractory. However, as the foregoing definition of "refractoriness" implies, the refractory material may be subjected to and is expected to resist not only high temperatures but a variety of other destructive forces incidental to its use. These include abrasion, impact, thermal shock, chemical attack, and high level loads at high temperatures. The various industrial applications of refractories represent an infinite variety of combinations and degrees of severity of these destructive forces, including high temperatures. Naturally, such a variety of application conditions leads to a need for a wide variety of refractory products to satisfy those conditions. The number of refractory products available is great enough that some form of classification is necessary to a discussion of refractories. Refractories may be classified in several ways, but the most suitable one is based on their general compositions and to lesser degrees on their physical condition and distinctive properties. The primary types of brick include aluminosilicate brick (fire clay and alumina), basic brick (magnesia and chrome ore, alone and in various combinations), silica brick, insulating brick, and special refractories (carbon, SiC, ZrO2, zircon, borides, and nitrides). Brick is, of course, preformed and usually is heat treated at high temperatures before use, but in some instances is unburned and/or chemically bonded, including the relatively new class of tar-bonded magnesia and/or dolomite brick. In addition to preformed refractories, another broad category includes the so-called specialty refractories, which are usually made in the same types as itemized for brick-bonding mortars and high temperature cements, hydraulic setting castables or refractory concrete, plastic firebrick, and ramming mixes. Refractory grains, such as fire clay and high alumina calcines, dead-burned magnesite and periclase, and dead-burned dolomite are also considered refractory products. Bricks are also classified on the basis of physical dimensions, as standard sizes and special shapes. The standard sizes are those which are of definite shape and design and are designated as 228.6 x 114.3 x 63.5 mm (9 x 4 ½ x 2 ½ in.) and 228.6 x 114.3 x 76.2 mm (9 x 4 ½ x 3 in.) straights and series. Bricks of nonstandard sizes are referred to as special shapes. These come about as a result of a particular need for a given furnace or for a particular application. Types and Classes of Refractories Fire Clay Refractories Classification: Fire clay refractories, as the name implies, are composed essentially of fire clay and/or calcined fire clay in varying proportions. The ASTM Standard Classification of Fireclay and High Alumina Refractory Brick, C27-70 (reapproved 1976), gives five classes of fire clay brick designated as super-

Jan 1, 1983

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?' precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.' These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.' In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y' intermediate precipitate, to- gether with some G.P. zones,' which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969

By AIME AIME

American Institute of Mining Engineers. (Organized in 1871, and Incorporated in 1905.) OFFICERS. For the year ending February, 1906. Directors JAMES GAYLEY (President), R. W. RAYMOND (Secretary), FRANK LYMAN Treasurer). T. A. RICKARD NEW YORK, N. Y. CHARLES H. SNOW NEW YORK, N. Y. R. W. RAYMOND NEW YORK, N. Y. (Terms expire February, 1906.) JAMES GAYLEY NEW YORK, N. Y. FRANK KLEPETKO NEW YORK, N. Y. FRANK LYMAN NEW YORK, N. Y. (Terms expire February, 1907.) JAMES DOUGLAS NEW YORK, N. Y. JAMES F. KEMP NEW YORK, N. Y. ALBERT R. LEDOUX NEW YORK, N. Y. (Terms expire February, 1908.)

Jan 1, 1906

By S. D. Dahlgren

ORDERED G.P. zones having the cesium chloride structure were found to exist in the bcc iron-rich grains of an Fe-Au-Cu alloy that had been supersaturated with approximately equal atomic percentages of gold and copper, and aged at 400° and 350°C. Streaks and superlattice spots in electron diffraction patterns revealed the presence of the ordered zones in the aged material. The ordered Ll2 structure is commonly found for precipitates in fcc metals (e.g., Ni3A1 in nickelL7') but it is uncommon to find precipitates in bcc metals having the cesium chloride structure. The formation of the G.P. zones caused age hardening of the grains. Samples containing 3.8 at. pct each of gold and copper (with the remainder being iron) were annealed at 95@ or 1125°C in quartz capsules and were quenched by breaking the capsules under water. X-ray diffraction patterns revealed two solid solutions in the quenched samples. One solid solution was bcc and the other was fcc. The microstructure consisted of iron-rich grains of 0.3 mm diam surrounded by a yellow gold-copper-rich grain boundary network. The Au-Cu phase diagram %hows continuous solid solubility of gold and copper with ordered phases forming below 410°C. None of the ordered Au-Cu phases have the cesium chloride structure. Both Fe-Au and Fe-Cu phase diagrams3 show extended miscibility gaps and only terminal solid-solution phases. Consequently, it is reasonably certain the iron-rich grains consisted of an a-phase terminal solid solution, and the grain boundary network consisted of a gold-copper-rich terminal solid solution. Lattice parameters of the quenched solid solutions were consistent with the suggestion that the quenched phases were terminal solutions. The lattice parameter of the bcc phase (2.879A) obtained upon quenching from 950°C was higher than that (2.866A) for pure iron. The fcc phase in this sample had a lower lattice parameter than that for a 50 at. pct Au and 50 at. pci Cu solid solution, i.e., 3.866 compared to 3.877A. The lattice parameter for the 50 pct Au and 50 pct Cu solid solution was interpolated from data for Cu-Au solid solutions.4 More gold and copper were soluble in iron at 1125°C than at 950°C as indicated by a 0.012A increase in the bcc lattice parameter for a sample quenched from 1125°C. After the alloy had been quenched from 950° and 1125°C, the bcc lattice parameters were 2.879 and 2.891A1 respectively G.P. zones having the cesium chloride structure-which formed during low-temperature aging—were detected by electron diffraction and observed with electron transmission microscopy. In Fig. 1, the asymmetrical streaks parallel to ( 100) directions indicate that platelike G.P. zones had formed parallel to (100) planes of the matrix. The direction of streak asymmetry shows that the bcc unit cell of the G.P. zones was larger than the bcc cell of the matrix. The ordered cesium chloride structure is indicated by low-intensity superlattice spots at 010 positions which are nonallowed for bcc structures. The superlattice spots are streaked; therefore they are from the G.P. zones and are not caused by rel-rod effects of a thin matrix phase. The appearance and size of the zones observed in electron transmission microscopy and the appearance of the asymmetrical streaks in the electron diffraction patterns for the Fe-Au-Cu alloy were the same as those observed for a similarly treated Fe-Au alloy.' Ordered G.P. zones were detected also for an Fe-Au-Cu sample aged only at 400°C. The production of the ordered cesium chloride structure zones by low-temperature aging of super-

Jan 1, 1968

By Ralph V. Higgins

This paper concerns the magnitude of the amount of supersaturation that occurs in an underground reservoir during the flow of oil and gas to wells and to the amount of undersaturation that occurs during repres-suring of an oil reservoir where some effective permeability to gas exists. The study is based on earlier laboratory findings of other investigators on the rate of diffusion of gas in oil as a function of the depth of oil. Utilizing these relationships and the principles of reservoir mechanics, a quantitative estimate of undersaturation and super-saturation was calculated. The results showed that the diffusion of the gas is rapid enough that for all practical purposes no supersaturation exists during the flow of oil to wells or undersaturation during repressuring in reservoir sands having some effective permeability to gas. The reason diffusion of the gas virtually keeps the oil saturated is the long time required in radial flow for oil to reach the well and the slow rate at which pressure in reservoirs is increased during repressuring. INTRODUCTION Knowledge of the phase relationships during flow of gas and oil in an underground reservoir is essential to operating the reservoir in the most efficient manner. In material-balance calculations and in fluid-flow studies, the oil is assumed to contain all the gas that it will dissolve at given temperature and pressure. Pressure-volume-temperature relationships are normally obtained in the laboratory using "bottom-hole" or combined samples of the reservoir fluids. In such laboratory determinations equilibrium is obtained between the oil and gas in the pressure cells by mechanical agitation. During the flow of oil and gas in reservoirs, however, no comparable agitation occurs to mix thoroughly these fluids to aid in effecting equilibrium between the two phases. During repressuring of a partly depleted underground reservoir, the gas is usually injected into the reservoir faster than the oil can absorb it; consequently, the oil is undersaturated. On the other hand, as the oil flows through the reservoir to the wells during producing operations the pressure decreases faster than the gas in solution can diffuse through the oil to the gas phase. The oil therefore is supersaturated with gas. Where the oil is undersaturated, gas diffuses away from the gas-oil interface, and where it is supersaturated the gas diffuses toward the interface. In either case the gas moves from a higher to a lower saturation. This report contains the results of a study of the factors influencing the degree of nonequilibrium of the phase relations of oil and gas in porous mediums during the flow of oil through reservoirs to wells and also during the injection of gas into partially depleted sands. Data from an underground reservoir are presented and the degree of supersaturation during the flow of the oil through the reservoir to the well is approximated. Also data from another reservoir are used and the degree of undersaturation during the repressuring operation is calculated. In addition, the flow rates of oil in laboratory experiments and in underground reservoirs are compared, as data from the laboratory are often used to interpret events in the reservoir, and the rates of flow influence appreciably the degree of nonequilibrium. Much of the contents of this report was prepared in 1943; but, because of other activities during and since the war, the manuscript was left untouched until 1952, when it was decided to include an estimate of the amount of undersaturation during repressuring as well as supersaturation during flow.

Jan 1, 1955

By Harvey T. Kennedy, Charles R. Olson

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

Jan 1, 1952

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968

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

The annealing behavior of a heavily cold-worked FeCo-V alloy has been studied at temperatures both above and below Tc, the critical temperature for ordering. It was found that re crystallization and grain growth can take place below Tc in the ordered state and that, in agreement with results for fcc alloys, order retards grain growth. The activation energy for pain growth is -55 kcal per mole in the disordered condition; it was not possible to assign a value to the activation energy for grain growth below Tc because the degree of order is changing rapidly over the temperature interval investigated. Precipitation of an fcc y phase was observed upon annealing the cold-worked alloy at temperatures of 675°C and below. SINCE it is known that diffusion constants are greatly affected by long-range order,' it is not unreasonable to anticipate that order will influence the diffusion-controlled phenomena of recrystallization and grain growth. In the course of a study of strain aging of ordering alloys around the composition Ni3Fe Vidoz, Lazarevic, and cahn2 noted that a disordered cold-worked alloy annealed at a temperature T1 just below Tc will order but not recrystallize; Tc is the critical temperature for order. The same alloy annealed at a temperature T2 just above Tc, or an alloy of different (nonordering) composition annealed at either T1 or T2, will recrystallize after equivalent amounts of cold work. Initially Selisskii and coworkers,3,4 who examined a series of cold-worked and annealed bcc Fe- Co alloys, reported that alloys forming the B2 FeCo super lattice could not be recrystallized below Tc. However in a later paper5 it was shown that FeCo ordered alloys could be recrystallized below Tc. Thus the first question to be answered by the present investigation was whether or not a heavily cold-worked Fe-Co-V alloy could be recrystallized below Tc. When it was found that the alloy would indeed re-crystallize below Tc, the influence of long-range order upon subsequent grain growth was studied. EXPERIMENTAL PROCEDURE The grain-growth measurements were made upon FeCo-2 pct V wire of 0.031 in. diam; the alloy was the same as that used in an earlier study of the mechanical properties of FeCO-v.6 The wire was produced by cold swageing and drawing a rod 0.125 in. diam that had been quenched into iced brine from 850°C to disorder the alloy; the initial grain size was 0.05 mm. Rates of grain browth were measured after isother-mally annealing the wire in the temperature range 675° to 825°C; T, is -720°C. Grain diameters were measured on the transverse cross section of the wires. The line-intercept method of determining the grain diameter was used; conventional light photomicrographs were taken when the grain size was greater than 10 . Carbon replicas were produced and examined in the electron microscope if the grain size was less than Dislocation configurations after recrystallization anneals were studied by electron transmission microscopy of foils produced by cold rolling a 0.125-in.-thick strip of the quenched material to 0.012 in. The foils, after heat treatments similar to the wire samples, were thinned by electropolishing in a chromic-

Jan 1, 1967

By L. E. Young

IT has been said the British Empire was built on British Coal. In all the postwar planning for Great Britain the necessity for producing cheap coal and the prosperity of the coal industry are given first consideration. On Jan. 23, 1945, there was released in London a "Report to the Colliery Owners" which had been awaited with great interest. This was entitled "A Plan for Coal" and was the recommendation of Robert Foot, chairman of The Mining Association (Colliery Owners), prepared at their request. Presentation of the "Plan" at this time is particularly significant as it is an answer to the demand for nationalization of the coal industry by the Labour Party and at the same time is a carefully considered program for postwar reconstruction, prosperity, and stability. In the words of Mr. Foot, If the coal industry for the first ten years after this war is to find itself in a situation similar to the one it occupied for the ten years following the last war, with its record of disputes, strikes, stoppages, short-time working, unemployment, and, with it all, a completely insufficient margin of profit, and all the insecurity and instability in our basic industry that was brought with them, it is goodbye to any real prospect of full employment, social security, and high standard of living. To present an elaborate review of the conditions which have brought to a crisis the unfortunate situation in the British coal industry is here unnecessary, but certain of the salient points

Jan 1, 1945

By S. J. Hruska, G. M. Pound

The critical supersaturations for appreciable nucleation rate of cadmium crystals on copper and glass substrates at 186°Kwere measured as a junction of thermal-beam energy over a range of source temperatures between 616" and 839OK. There was no effect of source temperature on critical super saturation. This implies that the adsmbate prior to nucleation is in thermal equilibrium with the substrate. THE deposition of metallic vapors on solid substrates has been found to exhibit a critical behavior in that the rate of formation of deposit increases markedly when the intensity of the vapor source is increased slightly.* Evidence of the ability of sub- where Je is the flux which would arrive if the substrate were equilibrated with bulk condensate at the adsorbate temperature. The following work was undertaken to test this hypothesis. A) Energy Exchange Between Metallic Vapor and Substrates. When a freely translating atom collides with a stationary solid body its energy and momentum undergo changes which determine whether the atom is reflected or adsorbed. An atom is considered to be reflected if it returns to a freely translating state after remaining under the influence of the body for only a time comparable to the period of oscillation of atoms on the surface. An atom which remains for a longer time is said to be in an adsorbed state. The parameter which describes the energy transfer occurring at the interface is the thermal-accommodation coefficient which may be defined in terms of energy as Ei = average energy of impingent atoms, Eeq = average energy of an emergent atom which has equilibrated with the substrate, and Eem = average energy of an emergent atom. If a temperature is assigned to each of these energies, we have at as defined by Knudsen.2 Since this allows no distinction between reflected and evaporated atoms, a more specific definition is introduced for the present purposes, namely 71 = probability that an impingent atom is transferred to an adsorbed state, aj = thermal-accommodation coefficient for reflected atoms, and aTc = thermal-accommodation coefficient for adsorbed atoms. During a time t,, the mean stay time, prior to evaporation the adsorbed atom (adatom) will interact with the substrate and this will have the net effect of transferring the adatom towards a state of

Jan 1, 1964

By T. A. Rickard

Freeman, the English historian, said that he had learned from Macaulay "never to be afraid of using the same word or name over and over again if by that means anything could be added to clearness or force. Macaulay never goes on, like some writers, talking about `the former' and `the latter', `he', `she', `it', and `they', through !clause after clause, while his reader has to look back to see which of several persons it is that is so darkly referred to". He might have learned also from Macaulay that a preposition makes a' feeble ending for a serious statement. How often do you hear `the former' and `the latter' in conversation? Good conversation is a guide not to be dis¬dained. When you must use `the latter', do not confuse it with `the last'. Cheap labor, cheap fuel, and cheap transport are essential, the latter [last] being particularly important in base-metal mining. The apparatus may be used to determine such gases as hydrogen sulphide, chlorine, oxides of nitrogen and some others, as well as sulphur dioxide. In the case of the latter two, etc. The two last mentioned are "sulphur dioxide" and "some others". He should have stated which two, and he should have avoided that wretched phrase "in the case of ". Pinning may be partly prevented by use of chalk, oil, or turpentine. The latter [last] is best. I "Partly prevented" is a poor phrase. `Prevented! is a word that does not lend itself readily to modification. He means `checked' or `corrected'.

Jan 1, 1931

Jan 1, 1961

By R. S. Wagner, H. Brown

Criteria for nucleation with the aid of twin planes during crystal growth from the melt are discussed. It is shown experimentally that bismuth crystals can grow from a subercooled melt in a twinned bismdtic form. A mechanism of growth based on the presence of at least me twin plane is proposed. It is well known that faceted growth can be observed in crystals grown from the vapor phase, dilute solutions, or from the melt. Faceted growth, in which the crystal is bounded by its slowest growing faces, will occur if the growth rate is strongly orientation dependent. The addition of atom layers on a facet plane can only occur by two-dimensional surface nucleation or with the aid of an imperfection. Nucleation with the aid of dislocations was proposed by rank' and observed to be of particular importance in crystal growth from the vapor phase. Nucleation with the aid of two-dimensional imperfections, notably twin planes, was suggested by stranski2,3 and Frank.4 A twin plane, terminating at the growth interface, can form a reentrant step at which nucleation can occur at a much smaller super-saturation (or supercooling) than required for two-dimensional surface nucleation. Nucleation by a twin plane usually results in a fast growth rate along a crystallographic direction parallel to the twin plane. Such a nucleation mechanism, based on the presence of a twin plane, has been used by Dawson5 to explain the growth and morphology of sheet-like crystals of paraffin n-hectane. In recent years more evidence was found that nucleation by twin planes occurs frequently in crystal growth from the vapor phase and from dilute solutions, for example, in cadmium,' barium titanate,7 silver,8 silicon9 and gallium arsenide.10 In crystal growth from a supercooled melt, however, nucleation by twin planes has so far only been observed in materials with the diamond or zinc blende structure. Bennett and Longini11 were the first to recognize the important role a single twin plane plays in the growth of germanium dendrites. Subsequently, it was found that a prerequisite for continued propagation of germanium dendrites is the presence of two parallel twin planes which form a self-perpetuating system of nucleation sites.12 Sili- con and some III-V compounds such as InSb also grow dendritically by twin plane nucleation. It appears that the following criteria must be satisfied in order that nucleation with the aid of twin planes can occur: A) The growth form of the material must be faceted." B) The formation of twin boundaries, by a fault in layer sequence during growth, by plastic deformation, or by an accidental meeting of properly oriented crystals, must be possible. C) Twinning must form a reentrant step where the twin boundary terminates at the faceted growth interface. D) These three conditions are necessary, but in certain cases not sufficient for continued crystal growth with the aid of a twin plane. Depending on interface morphology, a combination of more twin planes is sometimes required to form a self-perpetuating system of nucleation sites. This investigation was carried out with the idea in mind that nucleation with the aid of twin planes is a more general phenomenon and should occur in those materials, grown from a supercooled melt, which satisfy the criteria outlined above. It has been found that crystals of high-purity bismuth grown from a supercooled melt can grow by the aid of a twin plane. In the first two sections the faceted growth form and the twinning elements of bismuth are discussed. In the last section prismatic crystals of bismuth, which appear to grow with the aid of a deformation twin are discussed.

Jan 1, 1962

By J. G. McCullough

The paper is a general description of the U.S. lead and zinc industries as they are now compared to ten years ago and the effect of recent world-wide developments. Topics of interest concerning lead are the present and potential growth of the lead-acid battery business, the potential hazards of having one outlet for a major proportion of production, the expanding U.S. secondary lead production, the hardships of stringent hygiene and environmental regulations and the future supply and demand outlook. The present poor condition of the U.S. zinc industry caused by an oversupply of zinc metal - mostly in Europe - is discussed and also the shifting markets influenced by the automotive programs to reduce the weight of cars and the continuing high mine production due to the mixture of metals contained in the massive sulphide deposits which contain a major portion of the zinc metal reserves. This is all tempered by technical advances in die casting and the emphasis on the protecting of steel with zinc to prolong its useful life. New U.S. mine and smelter production facilities will be restrained due to lower cost foreign zinc from better grade ore deposits and the insistence by Governments for refining capacity to be constructed in the country that the ore is mined.

Jan 1, 1977

By F. Lynwood Garrison

Except in the old Catalan forge, or its modifications, attempts to make iron and steel directly from ore in a practical and economical manner have failed so frequently and completely that such schemes are looked upon with justifiable distrust. Without exception, all have failed from one cause or another, although in some instances every indication of a practical success was manifest in the beginning. It is, therefore, necessary to carefully examine and consider every detail affecting the process, or more properly, furnace, under consideration. This I have done to the best of my ability during a long visit to Russia last summer, and after satisfactorily observing the practical success of the furnace in the iron works of Count Stroganoff at Dobriansky in the Government of Perm, I decided to investigate as completely as possible the history of similar furnaces in Finland and Russia. These data, sifted and verified with the greatest possible care, form the substance of the present paper.* An illustration on page 321 of Percy's Iron and Steel shows the old type of Osmundssmide or harkugnar, which has been in use in Northern Europe since pagan times. Fig. 1 shows a furnace of this kind. It should, perhaps, more properly be called a high-bloomary furnace or forge, the Swedish word hark meaning bloom or loupe. It was with this type of furnace that Mr. Husgafvel began his experiments at Porsaskoski in 1875. Attempts to obtain better results with larger furnaces of this type were failures, as every bloom or loupe obtained necessitated blowing out the furnace with a consequent large waste of fuel. A larger furnace of course increased this waste with no corresponding advantage. A movable hearth of threeeighth inch iron, lined with a mixture of clay, quartz and lime, was next tried, but in consequence of the frequent repairs of this lining,

Jan 1, 1888