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By Michael Perch, Charles C. Russell

Nearly 7 5 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1943

By Michael Perch, Charles C. Russell

Nearly 7 5 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1943

By Potts N. L., Eilerts C. K., Summer E. F.

The second-order, nonlinear, partial- dillerential equation representing the transient radial flow of gas - condensate fluids in reservoirs has been integmted by using finite -dillerence equations and electronic computers. Effect was given to pressure -dependent permeability, viscosity, and compressibility and to distance-dependent permeability. The influence of a second-degree velocity term in the Darcy equation was investigated. Implicit methods were used and practical, convergent solutions were obtained with material balance to less than 6 x 10-4 for recovery of one- hall the reserve at constant flow rate. Integration results provide the productive period of a reservoir for a given constant rate and the fraction of the fluid initially in place that can be recovered in that period. The properties of a lean and a rich fluid are represented in a set of integrations designed to demonstrate the effect of different constant-recovery rates and significant variables emphasized one at a time. INTRODUCTION A method is needed for computing the availability or reserve of a gas in a formation, making use of all technical and engineering information that is pertinent. As a step in this direction, a program for computing transient linear flow1 was developed that utilizes principles of earlier finite-difference computing for a similar purpose2-4 and gives effect to significant pressure- and distance-dependent properties of reservoirs and their contents. The present paper pertains to transient, radial flow of gas-condensate fluids. In the partial-differential equation of flow, effect is given to the variables viscosity and compressibility,5 and also to permeability. Included in the study is the quadratic form of the Darcy equation of flow that has been the subject of field tests6 and that has been applied to a gas with constant properties in transient flow computing. 7 Inclusion in the differential equation of variable coefficients to represent properties greatly complicates the higher derivatives of the equation. Because it was impractical to make a required improvement in certain of the finite-difference derivatives by Taylor-series expansion, five-term derivatives were used in the implicit computing. Related methods were developed that can improve general facility in manipulating finite-difference equations. BASIC EQUATIONS PARTIAL DIFFERENTIAL EQUATION The basic partial differential equation for transient radial flow in the direction of decreasing radius is l_ a(vpr) _? .......(1) r gr at where r = radius, L v = apparent velocity aIong radius, L/t p = density, M/L3 t = time, t Ø = porosity, dimensionless. In this equation, only the porosity is regarded constant. The density is where p = pressure, m/Lt2 M = molecular weight of fluid, m T = constant temperature of fluid, T z(p) = pressure-dependent compressibility factor, dimensionless R = gas Constant, mL2/t2t. The physical boundary of the reservoir is at re, and the producing boundary is defined to be at tq with rq = re /200. By definition,

Jan 1, 1966

By Reynold Q. Shotts

INTRODUCTION THE small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive accumulation of coke in the form of "trees" or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow. most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of laboratories 1, 2, 3, 4, 5 are one method of approach to the problem of selecting stoker coals. As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simple measure of the tendency of a coal to form coke in a fuel bed. Although possessing all of the disadvantages of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects of swelling properties upon combustion. 7 Ostborg, Limbacher and Sherman, have shown that the test can predict, roughly, the tendency of coke to accumulate in the fuel bed of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1948

By J. E. Burke

RECENT investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen, Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: [D=Ktn [11] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Walker4 finds that, in alpha brass, the rate of growth falls off more rapidly than indicated by Eq I after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: [t, Hr i '_ III t„ = R \T, - ~) [2]] where t1 and t2 are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck.' The results obtained by Beck, Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and Hu6 later demonstrated experimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,10 Making implicit use of this assumption, several authors14,15 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parker' have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary, are on the average more surrounded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1948

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H'5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By Hjalmar W. Johnson

IT has long been accepted that blast-furnace practice varies to some degree with the coke used. While the qualities desirable in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blast-furnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: I. Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the production of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. FUNCTIONS OF COKE AND QUALITIES REQUIRED TO PERFORM THESE FUNCTIONS Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1941

By Robert E. Green

Formulae are given for calculating the modes of wave propagation in a single-crystdl specimen possessing a given crystallographic orientation. Such calculations lead to determination of the orientation factor appearing in the Granato-Lucke theory for the attenuation of these waves due to dislocation damping. A detailed treatment is given for the case of an aluminum crystal possessing the orientation having a maximum Schmid fac -tor of 0.5. FOR a number of years the attenuation of ultrasonic waves propagating in metals has been used to investigate various phenomena causing internal friction.Most of the experiments were performed on polycrystalline test specimens and the waves were assumed to be propagating in an isotopic medium. However Alers 6 in 1955 and more recently Hikata et at. Chiao and Gordon,8 and Swanson and Green 10 have used measurements of attenuation of ultrasonic waves to study internal-friction changes in single crystals. These authors were concerned with the energy losses experienced by the ultrasonic waves due to dislocation motion induced by plastic deformation of the crystals. Alers measured the attenuation of 7 mc per sec ultrasonic pulses propagating in zinc single crystals before, during, and after plastic deformation. Simultaneously he measured the time-dependent plastic strain at constant stress in order to study the correlation between this strain and attenuation. The crystals were oriented in such a way that the applied stress provided a direct shear on the slip plane, thus causing the deformation to proceed by slip on this plane. At the same time the high-frequency sound pulses were sent through the crystal perpendicular to the slip plane. He found that the attenuation of transverse waves, the stress vectors of which lie in the slip plane, was very sensitive to the deformation. The polarization of the particle displacements, associated with these waves, relative to the applied static shear stress, and hence the direction of slip, had no obvious effect on the results. The attenuation of longitudinal waves was affected by the deformation only when the slip plane was not perpendicular to the propagation direction. This indicated that the attenuation was caused by dislocations introduced by the deformation and moving only in the slip plane. Hikata et al. made simultaneous measurements of attenuation, velocity changes, and stress-strain relations on aluminum single crystals deformed in tension. Both longitudinal and shear waves were used, at frequencies of 10 and 13 mc per sec. They placed emphasis on the choice of propagation modes and polarization of the ultrasonic waves, such that interactions between these waves and dislocations on selected slip systems could be investigated. They also selected specimens possessing specific crys-tallographic orientations, which allowed investigation as a function of the number of equally favored slip systems under the applied stress. They found that, for symmetrical orientations, the change of attenuation decreases with the increasing number of equally favored slip systems, i.e., in the order

Jan 1, 1964

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By T. Saburi, C. M. Wayman

The massive and martensitic transformations in ß Cu-Ga alloys were studied by optical microscopy and by transmission electron microscopy and diffraction. These types of transformation are distinct and do not merge into one another. An internal fine structure due to stacking faults was found in both the massive phase (m) and the martensite, but the origin of the faults is believed to be different in each case. The faults in the martensite are due to the lattice invariant or "second" shear of the phenom-enological theory, while those in the are probably growth faults and deformation faults arising from the transformation volume change. Evidence is presented for ordering in the ß phase prior to transformation into martensite, and the crystal structures of and ß' and ßi martensites are discussed. THE results from some previous investigations1,2 have led to the suggestion that martensitic and massive transformations have certain common characteristics. It presently seems established that massive transformations like martensitic transformations are essentially diffusionless,1,2 but unlike martensitic transformations, when a new phase forms massively there is no shape change or surface relief.= If the massive-type transformation is crystallographically similar to martensitic transformations, one would expect a fine structure as a result of the lattice invariant shear4 which is a part of the transformation mechanism. The existence of such a fine structure (i.e., slip, twinning, or faulting), if any, can be verified by transmission electron microscopy, and thus the present investigation was undertaken to compare the internal structure of massively and martensitically formed phases in Cu-Ga alloys which were derived from a parent of the same composition. The transformation characteristics of ß Cu-Ga alloys were also studied. The bcc ß phase in the Cu-Ga system, Fig. 1, is stable above 616oc.' Depending upon the cooling rate, ß Cu-Ga alloys can undergo three different types of phase transformations. The ß phase of eutectoid composition (23.7 at. pct Ga) decomposes into the ? phase (hcp) and the phase (complex cubic) by means of a eutectoid reaction. When the cooling rate is increased so that the decomposition of 0 into [ and ? is suppressed, the ß phase transforms into a nonequilibrium hcp phase, herein denoted ?m by a process of very rapid growth called a "massive" transformation. At even faster quenching rates the massive transformation can be suppressed and the ß transforms martensitically. Massive transformations, apparently similar to those in the Cu-Ga system, have also been studied in the Cu-Zn2,6-8 and Ag-Cd systems.9 Definitive characteristics if the Massive Transformations in 0 Cu-Ga Alloys1 1) The most remarkable feature of the massive transformation in Cu-Ga is that there is no bulk composition change on transformation. According to Massalski,1 the resulting [, phase is a supersaturated extension of the equilibrium [ phase. The lattice parameters continue the trend exhibited

Jan 1, 1965

By L. F. Coffin

Monotonic tension and controlled cyclic-strain tests have been conducted on an annealed steel at various strain rates and temperatures in the weep range. Evidence of a strain-induced precipitate reaction abozle 500°C was determined from pronounced cyclic-hardening effects, increase inflow stress, inter granular fracture, drastic decrease in low-cycle fatigue resistance, and loss in tensile fracture ductility, as well as through electron-microscopy examination. It was found that strain rate as well as temperature had a pronounced effect on these observations. A parameter of the form P = T(7.95 - log ip) was determined, which was directly related to the ductility, defined either as the true strain at fracture in the case of simple tension, or as 2N 1/2 ? E p in the case of cyclic plastic strain. A highly satisfactory comparison of the cyclic life as measured and as computed from the ductility predicted by this parameter was obtained for a range of temperatures from 400° to 650°C and for crosshead speeds of 0.002 to 0.2 in. per min. MANY metals subjected to sustained loading at elevated temperatures derive resistance to creep from solid-state reactions of various alloying constituents. These reactions can be many and varied, and occur as a consequence of time and temperature according to reaction-rate principles. Strong evidence exists that many of these reactions are influenced by plastic strain, the argument being put forth that dislocations act as sites for nucleation and growth for the new phase.' Many examples can be cited where plastic strain during transformation influences the structure, and as a consequence affects the properties.2 The low-alloy steels serve as particularly good examples for investigating the effect which aging reactions have on resulting properties. Alloying elements such as carbon and nitrogen, and carbide formers such as manganese, chromium, molybdenum, and so forth, can, by the particular aging reaction which occurs, produce strengthening effects at various temperatures, and so endow strength to the alloy over a broad range of temperatures. These effects have been systematically studied by Glen both during creep3 and for constant strain-rate tension testing.4,5 The work of Glen is of considerable interest in connection with the present study, particularly in regard to the effect of various alloying additions on the true stress-strain curve and on fracture ductility at various elevated temperatures. He has shown that strain-age hardening occurred during plastic straining, which was quite specific both to the temperature of the test and to the alloying element involved. When strain-age hardening was noted at a particular temperature, a .minimum in reduction of area was also obtained. Provided the temperature for the minimum reduction of area exceeded 300°C, all minimum ductility fractures were found to be inter-crystalline in nature. For carbon steels containing molybdenum, two minima in reduction of area were noted, one occurring at 200° to 250°C, the precise temperature depending on the percentage of molyb-

Jan 1, 1964

By Yves Dardel

THE literature concerning the remelting of aluminum and its alloys is very rich. Unfortunately the greater part of the papers about this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification1,2 are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges and the atmosphere of the furnaces bring into the bath during the successive remeltings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, .. , if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H2, 02, H2O, C02, CO, CH4, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of Sieverts3 as a function of its partial pressure PH2 in the atmosphere [m = K _%/PH, [I]] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Röntgen and Braun4, Röntgen and Möller5, Bircumshaw6 and Winterhager7 have rendered it possible to determine the value of K, when the temperature is inferior to 1.000°K. One obtains: [log K = - 4,702.5 + 0.238 [2]] Besides its usual signification, the term PH2 represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is, when no gas exchange occurs between the two phases, the pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary occurs, the quantity of H2 should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature lowers, the internal pressure of H2 increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a maximum depending on the hydrostatic pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However, even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1947

By R. G. Vardiman, M. R. Achter

THERE has been interest recently in the conditions under which dislocation pipe diffusion may be observed. In order to extend the measurements to temperatures below Tm/2, where pipe diffusion becomes more important, a chemical sectioning technique was developed for silver single crystals which makes possible the removal of layers of 100A or less. The procedure is briefly as follows. Silver single crystals of 99.995 pct purity were cut in the form of discs t by 4 in., electropolished, and electropolated with Ag110 to about 1000A thickness. The thickness was determined by calibrating the activity with the weight of heavier platings, up to 10,000A. Both diffused and undiffused samples were sectioned in a two-step process. Reaction with a solution of iodine in alcohol formed a thin, even layer of AgI, which was then dissolved in a KCN solution. The reaction rate of the iodine solution varied slightly over a period of time, so that the thickness of the stripped layers, while quite even and regular for a given specimen, ranged from 65 to l00W for different specimens. This variation was checked by using a thickly plated standard with each run. Layer thickness was determined from undiffused samples by the point where the layer activity drops to half the maximum. This maximum intensity also provides, with appropriate corrections, the initial concentration per layer co. Because of the small penetration distances, it is necessary to use the exact solution of Fick's law for a source of finite thickness.' For a plating of thick- where c is the concentration at depth x. flj the error function, D the apparent diffusion coefficient, and t the time. The diffusion coefficient was obtained from the concentration-penetration data by extrapolating to x = 0 where c/co = erf h/2(Dt)1/2 Enough points were taken to impart confidence in the accuracy of the intersection, generally about ten layers. Four temperatures were used as in Table I. For best accuracy, t and h were chosen to give values of the parameter (Dt)1/2/h between 1.0 and 1.7. A typical concentration-penetration curve is shown in Fig. 1. The diffusion coefficients calculated from Eq. [I] are plotted in Fig. 2. For comparison, the high-temperature data of Tomizuka and sonder 2 which go down to 630°C are plotted as the solid line 2(a) from their expression D = 0.40 exp (-44,090/RT). Also for comparison, the lowest temperature point of Hoffman and Tumbull3 is plotted. It is apparent that our data diverge appreciably from the high-temperature extrapolation by 373°C. A better straight line fit for the low-temperature portion is obtained by subtracting the extrapolated volume diffusion coefficient from the apparent. or measured coefficient, and plotting the difference, curve (h) of

Jan 1, 1970

By Alfred H. Bell, George V. Cohee

In 1941 Illinois produced 134,139,000 bbl. of oil, or 9.5 per cent of the total for the United States, and ranked fourth among the states. The production for 1941 declined 9.2 per cent from the previous year's total of 147,647,000 bbl. Daily average production for 1941 was 366,000 bbl. At the beginning of the year daily production was slightly more than 326,000 bbl. and it remained at appoximately that amount until June, when there was a slight increase. The increase continued until the peak of 431,260 bbl. daily was reached for the week ending Oct. 4. Daily average production at the end of the year was approximately 387,500 barrels. The increased production during the last half of 1941 was largely due to the rapid development of the Johnsonville field, Wayne County, the Rural Hill field, Hamilton County, and the Benton field, Franklin County—new fields discovered in the current year (Fig' 1)—and the Woodlawn pool, discovered in 1940. Discoveries In 19 counties in southern Illinois, 44 new fields were discovered in 1941 (Fig. 2 and Table 2), and extensions to 40 fields were successfully completed (Table 3). At the end of the year there were 10,496 wells in the fields discovered since Jan. I, '937, as compared with 71965 wells at the end Of '940. The area proved for production in the new fields increased from 78,040 acres at the beginning of 1941 to 97,483 acres at the end of the year (Table I)—an increase of 19,433 acres, of which 9,955 acres are in the fields discovered during the current year, and the remainder of 9,478 acres in extensions to pools discovered earlier. Drilling During the past year, 3838 wells were completed in Illinois (Table 4), of which 2912 were oil producers, 13 were gas producers and 913 were dry holes; 76 per cent of the wells drilled were producers. Of the total number drilled, 591 wells are classified as "wildcat" and of these 84 (1 in 7) were successful in obtaining production. The results of an investigation to ascer-tain the reason for the locations of the wildcat wells are set forth in Table 5. Of the 591 wildcat wells, the 292 known to have been located by scientific methods were 21.6 per cent successful. The total footage of wildcat wells drilled in 1941 was 1,341,743 ft., of which a total of 216,995 ft. was drilled in successful wells. Exploration MEthods Subsurface geology and geophysics, largely the reflection seismograph, are still the principal methods used in exploration and development in the state. The number of seismograph parties operating throughout the year was as follows: seven parties on Jan. I, 1941; five on Apr. I; four On July I; eight on Oct. I; fifteen on Jan. 1: 1942.

Jan 1, 1942

By Alfred H. Bell, George V. Cohee

In 1941 Illinois produced 134,139,000 bbl. of oil, or 9.5 per cent of the total for the United States, and ranked fourth among the states. The production for 1941 declined 9.2 per cent from the previous year's total of 147,647,000 bbl. Daily average production for 1941 was 366,000 bbl. At the beginning of the year daily production was slightly more than 326,000 bbl. and it remained at appoximately that amount until June, when there was a slight increase. The increase continued until the peak of 431,260 bbl. daily was reached for the week ending Oct. 4. Daily average production at the end of the year was approximately 387,500 barrels. The increased production during the last half of 1941 was largely due to the rapid development of the Johnsonville field, Wayne County, the Rural Hill field, Hamilton County, and the Benton field, Franklin County—new fields discovered in the current year (Fig' 1)—and the Woodlawn pool, discovered in 1940. Discoveries In 19 counties in southern Illinois, 44 new fields were discovered in 1941 (Fig. 2 and Table 2), and extensions to 40 fields were successfully completed (Table 3). At the end of the year there were 10,496 wells in the fields discovered since Jan. I, '937, as compared with 71965 wells at the end Of '940. The area proved for production in the new fields increased from 78,040 acres at the beginning of 1941 to 97,483 acres at the end of the year (Table I)—an increase of 19,433 acres, of which 9,955 acres are in the fields discovered during the current year, and the remainder of 9,478 acres in extensions to pools discovered earlier. Drilling During the past year, 3838 wells were completed in Illinois (Table 4), of which 2912 were oil producers, 13 were gas producers and 913 were dry holes; 76 per cent of the wells drilled were producers. Of the total number drilled, 591 wells are classified as "wildcat" and of these 84 (1 in 7) were successful in obtaining production. The results of an investigation to ascer-tain the reason for the locations of the wildcat wells are set forth in Table 5. Of the 591 wildcat wells, the 292 known to have been located by scientific methods were 21.6 per cent successful. The total footage of wildcat wells drilled in 1941 was 1,341,743 ft., of which a total of 216,995 ft. was drilled in successful wells. Exploration MEthods Subsurface geology and geophysics, largely the reflection seismograph, are still the principal methods used in exploration and development in the state. The number of seismograph parties operating throughout the year was as follows: seven parties on Jan. I, 1941; five on Apr. I; four On July I; eight on Oct. I; fifteen on Jan. 1: 1942.

Jan 1, 1942

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.' These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,' from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941