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By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

By C. W. Allen, B. D. Cullity, H. S. Choi

The torsional deformation of aluminum and magnesium crystals is investigated, with particular reference to the dependence of proportional limit on crystal orientation. The proportional limit is found to be governed by the average value of the resolved shear stress on the most highly stressed slip systems, but the proportional limit does not strictly obey a critical-resolved-shear-stress law. The behavior of a cylindrical single crystal stressed in tension is well known: plastic flow begins when the resolved shear stress on the most highly stressed slip system reaches a critical value. There is much less understanding of the effect of torsion on such a crystal and on the way in which the critical-resolved-shear-stress law should be applied to torsional deformation. In the present paper particular attention is paid to the dependence of plastic yielding on crystal orientation and lesser attention to the mechanism of flow after yielding has occurred. New work on aluminum and magnesium crystals is presented, and previous results obtained in this laboratory on magnesium1 are re-examined. STRESS DISTRIBUTION The problems involved in torsional deformation of single crystals are due entirely to the complexity of the stress distribution. In tension, if loading conditions are perfect, the shear stress on any particular slip plane is completely uniform over the entire area of that plane. In torsion, on the other hand, the stress on any selected plane in a particular direction varies not only from center to edge of the specimen but also around its perimeter. It is convenient to express the stress at any point in terms of t0, which is the shear stress acting at the surface of a cylindrical specimen on a plane normal to the axis and in a direction tangential to the cylinder. At point P of Fig. 1 this stress acts in the direction of axis 2 and is given by To = 2T/pr3 [1] where T is the applied torque and r the specimen radius. This stress can be resolved on any chosen slip system, and details are given in the Appendix. Let P be the point on the specimen surface where the stress is to be evaluated; P is defined by its angular distance A from an arbitrary reference line through 0 normal to the axis. his line is usually taken as the direction of incidence of the X-ray beam used to determine the crystal orientation.) Then the shear stress t, acting at P in direction Dona plane whose normal is N is given by Ts/TO = sin ? 0, cos ?d sin (?0, - ?) + cos ?, sin ?d sin (?d - ?) [2] where 0, and Od are the angles between N and D, respectively, and the axis, ?0 and ?d are the angles between the projections of N and D, respectively, on the transverse plane and the reference line through 0. By means of Eq. [2], the stress 7, acting in any given slip direction can be computed. In the previous work on magnesium1 only gross slip tangential to the specimen surface was considered, and this

Jan 1, 1963

By F. V. Lenel, J. A. Dromsky

The influence of thermal and mechanical treatments upon the elevated-temperature stability, the microstructure, and the mechanical properties of aluminumaluminum oxide alloys is investigated. Compacts from atomized and flake aluminum powders were sintered at temperatures just below the melting point of aluminum in a vacuum of 10-4 Torr for several hours and were then hot-extruded. During this treatment the hydrated oxide present on the surface of the powder particles decomposes, the water vapor produced reacts with the aluminum forming additional oxide, and the hydrogen developed is removed by diffusion to the surface. Extrusions of compacts so treated are stable at temperatures up to the melting point of aluminum and do not form blisters and internal defects typical of extrusions from untreated powder. Electron micrographs of extrusions from unsintered compacts show long parallel oriented platelets typical of the IN previous investigations1,2 the properties and structure of aluminum alloys were described which had been produced by cold compacting aluminum powder and then hot pressing and extruding the compacts. Both the structure and the properties of these alloys differ significantly from those of commercially produced aluminum-aluminum oxide alloys. When commercial alloys are produced, they are given a sintering treatment in air at about 600°C between cold compacting and hot pressing.3 During this treatment the hydrated oxide, which forms the coating on the aluminum-powder particles from which the alloys are prepared, is decomposed.4 The chemically bound water which is released reacts with the aluminum and forms aluminum oxide and hydrogen. Most of the hydrogen is eliminated by hydrated oxide skins on the original powder particles, while the oxide particles in extrusions from sintered compacts are broken up. The strength of extrusions from treated powder is somewhat lower, but their ductility is considerably improved over that of extrusions from untreated powder. The slip-trace patterns on electron microgvaphs of extrusions which had been strained in tension before replication indicated that the grain size of the extruded alloys was approximately the same as that of the original powder particles. Coarse-grained alloys were produced by severe cold work and annealing of the extrusions. They have significantly lower room-temperature strength, but about the same ductility as the vacuum-sintered fine-grained alloys. The size and shape of oxides in the coarsegrained alloys is similar to those of the fine-grained alloys, but the particles are somewhat more uniformly distributed. diffusing to the interior or exterior surfaces of the compact, but it is difficult to eliminate all of it because the solubility of hydrogen in solid aluminum is very low even near its melting point. Extruded alloys which are not sintered before hot pressing and extrusion appear quite sound upon metallo-graphic examination, but develop severe surface blistering and internal fissuring when they are heated to elevated temperatures after extrusion. Fissures and blisters have been observed even in commercial alloys which had been sintered in air, although they are much less severe.' Because of the importance of this sintering treatment it was studied in this investigation in a modified form, using vacuum sintering rather than sintering in air, to insure more complete elimination of occluded hydrogen. The technique is described and the effect of the treatment upon the structure of the alloys is documented. It has been known for some time that extruded aluminum-aluminum oxide alloys are very finegrained, but an exact delineation of grains in electron micrographs has not been possible. In the conventional metallographic-etching techniques etchants attack the interface between the second-phase particles and the matrix in the alloys much

Jan 1, 1964

By R. J. Lutton

Empirical data from 91 rock excavations have been used to construct a family of slope curves on a chart relating excavation height and inclination. The highest and steepest slopes from each excavation are plotted and connected by a line. The 31 1ines appear to establish one or two geometrical slope fields through which the curves are projected. The curves apparently represent a lumped eflect of many factors too complex to be considered individually. Important factors such as geological structure or ground-water conditions can dominate the picture, but where these factors do not overshadow others, the slope chart should be useful for estimating or checking optimum inclination. The U.S. Army Corps of Engineers (USAE) has been engaged since 1962 with the U.S. Atomic Energy Commission in a joint research program to develop nuclear excavation technology. The Corps is responsible for collecting the requisite data on engineering and construction problems associated with nuclear excavation. The ultimate objective is to develop a capability to use nuclear explosives as a construction tool on public works projects such as harbors and canals. The present study on empirical inclination-height curves for conventionally excavated slopes is an outgrowth of an investigation' sponsored by the USAE Nuclear Cratering Group on applicability of data from existing excavations in establishing guides for engineering judgment in crater excavation. Data were generously contributed by over 50 mining companies among other organizations. Inasmuch as several companies preferred that their contribution be anonymous, all data are treated so here. Some Factors Affecting Stability Many factors affect or are suspected of affecting the stability of excavated slopes, e.g., adverse structural orientation, degree of structural ordering, ground water, climatic conditions, mechanics of excavation, and plan-profile configuration. Such factors are lumped together in developing a slope chart. Obviously geological structure and ground water can overshadow all other factors. Where such is the case, the simplification of slope charts may give an erroneous picture (not conservative enough). A further complication results from the fact that the concept of stability may vary according to the use of the excavations. For example, slope adjustments that would be regarded as failure in a powerhouse excavation, might be tolerable in a mining operation. Mine slopes are continually being modified by further excavation, and instability that would develop in a similar permanent excavation slope over a period of years might not have time to develop in a mine. Inclination vs. Height Charts Charts of inclination vs. height for particular formations or conditions have been used in the past as an aid for designing excavation slopes. Some of these have been based upon empirical analyses of collections of data and experience. MacDonald" and Lane have presented slope tables and charts for excavated and natural slopes in relatively weak sandstone and shale. Coates' has shown an inclination-height chart for slopes in incompetent rock. Most organizations have developed slope design criteria which relate bench widths, heights, and inclinations to use in various rocks. Slope data collected in present studies can be similarly used to develop inclination-height charts; however, a plot of all slopes on such a chart shows very little because of the wide spread of the data. Reasons for the dispersion of points are: (1) many slopes are not carried at optimum inclination, particularly in mines where maintaining roadways and following irregularities of ore bodies are more important than achieving steep inclinations; (2) many engineers and geologists with varied backgrounds and viewpoints have been involved in designing these slopes; and (3) each slope is characterized by a unique combination of factors affecting stability and in turn optimum inclination. Significant curves can sometimes be constructed where the points can be grouped into related clusters from the same excavation. The essence of this approach appears when only two slopes from each excavation are considered—the highest slope and the steepest slope, connected by a line segment (Fig. 1). This reduces considerably the usable data because in many cases only one of these two slopes is available. Nevertheless, the concession seems justified. Construction of Slope Curves Ninety-one pairs of points and connecting line segments were assembled in this study. The line segments were assumed to approximate a geometrical slope field (Fig. 2), and a family of curves has been visually projected through to represent the slope field. It should be

Jan 1, 1971

By Albert E. Reed

The development of the modern highspeed vibrating screen, together with the increasing availability of long-lasting stainless-steel screen cloth for relatively fine-mesh separations, means that more screen circuits will be used in the future. It seems pertinent therefore to examine a few characteristics of screen-circuit products, and especially the points of difference as compared with products of classifier circuits. The most noticeable change that takes place when substituting screening for classification in a grinding circuit is a substantial drop in the circulating load, owing to the greater ease with which the "fines" leave the circuit. Where circulating loads of 500 to 600 per cent are considered fairly normal in classifier grinding circuits, the grinding circuit equipped with screens for equivalent work will have a circulating load of only 20 to 75 per cent. As a result, the products of screen circuits will show a minimum of overgrinding or sliming as compared with a classifier circuit. The desirability of this characteristic will naturally vary according to the metallurgical requirement in each case. Because screen separations make a sharper division according to particle size, the products of screen circuits can be expected to show greater crowding of particles near the point of separation. These changes in product characteristics are so important that other factors, both in the grinding and concentration processes must be adjusted if the operator is to take full advantage of the increased tonnages and higher efficiencies available to him through the use of the screen circuit. One factor that too often is overlooked when changing to screen circuits is the importance of adjusting the ball-mill or rod-mill charge, to compensate for: (I) increased tonnage of new feed, (2) decreased circulating load, or (3) more granular character of feed. These same factors should also be taken into consideration for their effect on the various types of concentration or flotation equipment that may follow the screen circuit. Over a period of years, this equipment has generally been designed and adjusted to the product of the classifier, therefore it seems obvious that some research on the adjustment and adaptation of concentrating and flotation equipment to screen-circuit products will be most profitable to the operators. To illustrate the points mentioned above, the results from three recent installations follow, with data on the comparative characteristics of screen and classifier circuits. A range of separation from 10 to 48 mesh has been chosen, using two general types of screening equipment and two types of classifiers. The first of the installations of which the results are to be examined is that of an iron-ore installation where eastern magnetite was being concentrated prior to sintering. Fig. I shows the original grinding circuit, using classification, while Fig. 2 shows the same circuit equipped with a

Jan 1, 1947

By Albert E. Reed

The development of the modern highspeed vibrating screen, together with the increasing availability of long-lasting stainless-steel screen cloth for relatively fine-mesh separations, means that more screen circuits will be used in the future. It seems pertinent therefore to examine a few characteristics of screen-circuit products, and especially the points of difference as compared with products of classifier circuits. The most noticeable change that takes place when substituting screening for classification in a grinding circuit is a substantial drop in the circulating load, owing to the greater ease with which the "fines" leave the circuit. Where circulating loads of 500 to 600 per cent are considered fairly normal in classifier grinding circuits, the grinding circuit equipped with screens for equivalent work will have a circulating load of only 20 to 75 per cent. As a result, the products of screen circuits will show a minimum of overgrinding or sliming as compared with a classifier circuit. The desirability of this characteristic will naturally vary according to the metallurgical requirement in each case. Because screen separations make a sharper division according to particle size, the products of screen circuits can be expected to show greater crowding of particles near the point of separation. These changes in product characteristics are so important that other factors, both in the grinding and concentration processes must be adjusted if the operator is to take full advantage of the increased tonnages and higher efficiencies available to him through the use of the screen circuit. One factor that too often is overlooked when changing to screen circuits is the importance of adjusting the ball-mill or rod-mill charge, to compensate for: (I) increased tonnage of new feed, (2) decreased circulating load, or (3) more granular character of feed. These same factors should also be taken into consideration for their effect on the various types of concentration or flotation equipment that may follow the screen circuit. Over a period of years, this equipment has generally been designed and adjusted to the product of the classifier, therefore it seems obvious that some research on the adjustment and adaptation of concentrating and flotation equipment to screen-circuit products will be most profitable to the operators. To illustrate the points mentioned above, the results from three recent installations follow, with data on the comparative characteristics of screen and classifier circuits. A range of separation from 10 to 48 mesh has been chosen, using two general types of screening equipment and two types of classifiers. The first of the installations of which the results are to be examined is that of an iron-ore installation where eastern magnetite was being concentrated prior to sintering. Fig. I shows the original grinding circuit, using classification, while Fig. 2 shows the same circuit equipped with a

Jan 1, 1947

By Thomas Leonard Watson

Sulphide ore-bodies of more or less lenticular shape occurring in metamorphic crystalline schists, gneisses, and slates, and conforming closely in strike and usually in dip to the inclosing rock, have been recognized and described along the Atlantic seaboard from Quebec to Alabama. The ore-bodies do not entirely conform, in all cases, to the structure of the inclosing schists, but they sometimes cut across the foliation in dip, though conforming more closely with the direction of strike. In composition the principal sulphide mineral is usually py-rite or pyrrhotite, or both, accompanied by copper, frequently gold, and almost always some sphalerite and galenite. Other metallic ores are, so far as these sulphide bodies have been investigated, less common; silver is not uncommon, and in some of the pyrrhotite masses nickel is present in quantity sufficient to be commercially valuable. Cobalt frequently accompanies the nickel, usually in smaller amount, and the two vary much in relative proportion. Quartz and calcite are probably the most common of the non-metallic minerals. A number of silicate minerals are frequent representatives in one place or another ; garnet, am phi-bole, biotite, pyroxene, zoisite and others. The sulphide bodies of Virginia, comprising both pyrite and pyrrhotite, are among the most extensive along the Atlantic seaboard. Among the pyrite bodies may be mentioned the well-known and extensively worked mines of Louisa and Prince William counties, located on the main pyrite belt (A, Fig. 1) of the middle and northern, eastern Piedmont region in Virginia, and among the pyrrhotite bodics is the famous " Great Gossan Lead" (13, Fig. 1) of the Floyd-Carroll-Grayson coun-

Jan 1, 1908

By F. D. Rosi

IN the production of single crystals by the Bridg-man method of solidification from the melt in vacuum at a crucible lowering rate of 0.25 in. per hr, a cellular structure was frequently observed in copper and copper-base alloys at the terminal surface of the as-cast crystals (i.e., the surface representing the last portion of the crystal to solidify). The geometrical form of this structure varied from crystal to crystal, but, in general, could be classified as either hexagonal or quadrilateral. Fig. 1 shows examples of this cellular structure, which is similar to that reported by Buergerl and, more recently, by Pond and Kessler&apos; and Rutter and Chalmers. In the micrographs of Figs. lb and c, the cubic structure in the alloy crystals is obscured somewhat by excessive surface evaporation in the final stages of solidification. X-ray orientation studies indicate that the traces outlining the various geometrical forms correspond to octahedral planes, which are the planes of greatest reticular density in the face-centered cubic lattice. It would appear from this that the view first propounded by Bravais,4 that the surface energies and normal growth velocities of the different crystal planes are inversely proportional to their reticular densities, applies to this cellular structure, since those surviving are the planes of greatest atomic density. Thus, the observed variation in the geometrical form of this structure in crystals of different orientation is readily understandable from the distribution of the (111) planes in the standard {111}, (1101, and (1001 stereographic projections. Depending upon whether the crystal axis (i.e., the direction of crystallization) coincides with a <111>, <111>, or <100> direction, the cellular structure viewed from a surface perpendicular to the crystal axis will consist of a network of regular hexagons, skewed hexagons (with interfacial angles of 110" and 125"), or cubes, respectively. It follows, moreover, that off-orientations from these principal directions will yield modifications of these three basic geometric configurations. In this connection, it is interesting to note that the bounding planes of the hexagonal structure observed in tin by Rutter and Chalmers3 showed no preferred orientation.

Jan 1, 1954

By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A&apos; and Stage B&apos;. Stage A&apos; type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B&apos; type from -80 x 10-6 to -800 x 10&apos;6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A&apos; and Stage B&apos; deformation are briefly reviewed. 1) Stage A&apos;. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10&apos; cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B&apos; there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965

By Charles M. Packer, Oleg D. Sherby, Roy H. Johnson

Originally round tensile specimens of a eutectic Zn-A1 alloy develop elliptical cross sections during superplastic deformation. This observation, coupled with a detailed study of the microstructure and preferred orieniation, suggests that crystallographic slip and continuous grain boundary migration or re-crystallization are important processes during super-plastic deformation. In spite of the extensive activity in superplasticity1-15 and the numerous explanations proposed, no single model has had universal acceptance. It has been established, however, that the general requirements for superplastic extension of two-phase alloys include an extremely fine, stabilized grain size of the order of a few microns, a temperature about equal to or greater than one-half the melting point, a critical range of strain rate, and a similarity in the mechanical strength of the major phases. The proposed models can perhaps best be characterized in terms of the important phenomena associated with them. These phenomena include: phase instability,1 diffusional creep by volume diffusion3 or grain boundary diffusion4,5 slip and continuous grain boundary migration or recrystalliza-tion,= grain boundary Sliding,7-9,13,14 and dislocation glide.&apos;5 In this paper, experimental observations will be reported which support a model involving slip and continuous grain boundary migration or recrystalliza-tion. Specifically, a correlation will be made between this model and the development of elliptical cross sections as originally round specimens are superplas-tically deformed. For the most part, superplasticity studies have been conducted with eutectic or eutectoid alloys. Probably the most thoroughly studied material has been the monotectoid Zn-A1 alloy.1,2,6,12,13,15 No attention to the eutectic Zn-A1 alloy has previously been reported, and the results discussed in this paper represent part of a general study of the superplastic properties of this alloy. MATERIALS The alloys used in this investigation were prepared by melting appropriate quantities of 99.99+ pct A1 and 99.999 pct Zn in air, mixing, and pouring into a water- cooled stainless-steel mold. Wet-chemical analysis was conducted with each heat of alloy prepared, using the procedure of Fish and smith.16 The composition of the eutectic alloy was 95.1 wt pct Zn. Ingots about 2 in. thick were rolled to 0.4-in. plate at about 300°C with a reduction of 5 to 10 pct per pass. Specimens were machined from the plate with the tensile axis parallel to the rolling direction. The specimens were round, with 0.150-in.-diam, 1.25-in.-long gage length, and 0.25-in.-diam threaded grip sections. EXPERIMENTAL PROCEDURE Specimens were mounted inside a uniform-temperature quartz tube which was surrounded by a double elliptical radiant furnace with a 12-in.-long uniform-temperature hot zone and a low thermal capacity. The tube extended through the top and bottom of the furnace and permitted rapid quenching of the loaded specimens when quickly filled with cold water at the conclusion of the test. The quench precluded any effects on specimen microstructure from a normal, slow cool. Constant stress was applied to test specimens by suspending a load on a constant stress cam of the type described by Hopkin.17 The design of this cam permitted application of a constant stress for elongations up to 200 pct. For greater elongation, approximately constant stress conditions were maintained by systematically reducing the load manually. RESULTS As part of an investigation of the superplastic properties of the eutectic Zn-A1 alloy, evidence was obtained for the development of elliptically shaped cross sections as originally round specimens were extended. For example, after an elongation of about 100 pct, a round specimen with an initial diameter of 0.150 in. became elliptical with major and minor axis of 0.128 and 0.88 in., respectively. Photographs are presented to illustrate the ellipticity developed during superplastic deformation, Fig. 1. The specimen shown was deformed at a stress of 500 psi, at a temperature of 285°C, and a strain rate of 2.28 x 10-2 min-1. The strain-rate sensitivity exponent* was measured at *The strain-rate sensitivity exponent, m, is defined as d In o/d In c where o is the steady-state flow stress and E is the strain rate. this temperature and in the strain rate range 10"3 to 10-1 min-1 was found to be about 0.5. This value is typical of those observed with superplastic materials. The material studied exhibited negligible strain hardening during superplastic deformation, the creep rate remaining constant under constant stress and temper-

Jan 1, 1969

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,&apos; it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:&apos; log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0&apos; systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick&apos;s first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By J. W. Halley, T. S. Washburn

Rimming steels derive their name from their action during solidification in the molds. As a result of incomplete deoxidation, gas is evolved during freezing, and the metal has a characteristic rolling action. The metal rises along the mold walls and descends in the center of the ingot. This action keeps the top of the ingot open and the advancing rim of solid metal can be seen. The rim grows until the rolling action is insufficient to prevent the top of the ingot from freezing or until the action is stopped by capping the ingot with a heavy plate. The violence of the reaction and its characteristics, such as growth or drop in the molds, are determined by the composition, the furnace practice, and the deoxidation in the ladle and in the molds. Though rimming steels represent a large proportion of the amount of plain carbon steel made, they have received comparatively little attention in the technical literature. The manufacture of rimming steels has been described by Hibbard,1,2 Fleming,3 Pierce4 and Jackson.5 The reactions occurring during rimming have been considered from the theoretical point of view by Chipman and Samarin.? The structure of rimmed-steel ingots has been discussed by Nead and one of the present authors6 Meyer: in studying segregation, investigated the distribution of carbon, sulphur and phosphorus in rimmed-steel ingots by analyzing the rim and core of blooms. In their studies of segregation, the Joint Committee of the Iron and Steel Institute and the British Iron and Steel Federation9 studied distribution in one billet and one ingot of rimmed steel. A detailed study of the distribution throughout the ingot has not been published. The present investigation was undertaken to determine accurately the distribution of carbon, manganese and sulphur in normal rimmed ingots and the general distribution of other common elements present. The study included some work on the effect of pouring conditions and furnace practice on the distribution, though there is still much to be done in this direction. The structure of a rimmed ingot that has been split by dynamiting and a schematic diagram of the zones in the ingot are illustrated in Fig. 1.

Jan 1, 1938

By J. W. Halley, T. S. Washburn

Rimming steels derive their name from their action during solidification in the molds. As a result of incomplete deoxidation, gas is evolved during freezing, and the metal has a characteristic rolling action. The metal rises along the mold walls and descends in the center of the ingot. This action keeps the top of the ingot open and the advancing rim of solid metal can be seen. The rim grows until the rolling action is insufficient to prevent the top of the ingot from freezing or until the action is stopped by capping the ingot with a heavy plate. The violence of the reaction and its characteristics, such as growth or drop in the molds, are determined by the composition, the furnace practice, and the deoxidation in the ladle and in the molds. Though rimming steels represent a large proportion of the amount of plain carbon steel made, they have received comparatively little attention in the technical literature. The manufacture of rimming steels has been described by Hibbard,1,2 Fleming,3 Pierce4 and Jackson.5 The reactions occurring during rimming have been considered from the theoretical point of view by Chipman and Samarin.? The structure of rimmed-steel ingots has been discussed by Nead and one of the present authors6 Meyer: in studying segregation, investigated the distribution of carbon, sulphur and phosphorus in rimmed-steel ingots by analyzing the rim and core of blooms. In their studies of segregation, the Joint Committee of the Iron and Steel Institute and the British Iron and Steel Federation9 studied distribution in one billet and one ingot of rimmed steel. A detailed study of the distribution throughout the ingot has not been published. The present investigation was undertaken to determine accurately the distribution of carbon, manganese and sulphur in normal rimmed ingots and the general distribution of other common elements present. The study included some work on the effect of pouring conditions and furnace practice on the distribution, though there is still much to be done in this direction. The structure of a rimmed ingot that has been split by dynamiting and a schematic diagram of the zones in the ingot are illustrated in Fig. 1.

Jan 1, 1938

By E. J. Schmitz

This novel safety-lamp, which was first introduced in some of the German coal-mines in 1882, at once attracted general attention in the coal-districts of Europe. Objections which arose during the early stages of its use at the mines have gradually died away with the increase of experience in handling the lamp 011 the part of the miners, and the continual efforts to perfect it on the part of its inventors. Wolf&apos;s lamp has rapidly surpassed all its rivals, and has already a greater distribution on the Continent than any one of its older sisters. In the course of two and a half years, the manufacturers have sold 25,000 of the lamps, besides remodelling several thousand rapeseed-oil lamps. This great success, which of itself speaks loudly enough as to the superiority of the Wolf benzine-lamp, is corroborated by both official and private reports, which all agree in pronouncing this lamp the best yet brought forward. It was described in a paper by Mr. Eugene B. Wilson, read at the Chicago meeting of the Institute, in May, 1881,* in which its salient merits were briefly but clearly indicated. Every previous improvement of the original Davy lamp has been directed to one or more of the following main points: 1. Light of greater and more uniform intensity. 2. Freedom from smoke or soot, which clogs the gauze and other parts of the lamp. 3. A greater safety and sensitiveness in the presence of firedamp. 4. An illuminating material which, satisfying the foregoing conditions, should be also cheap. 5. A lock which could not be opened in the mine by the miner. 6. An arrangement for lighting without opening the lamp. 7. An arrangement for changing the size of the flame in the closed lamp, to supersede the picker, the danger from which is explained in Mr. Wilson&apos;s paper, already cited. It may safely be said that wolf&apos;s lamp was the first to secure all these objects. The adoption of benzine instead of rapeseed-oil (previonsly the best illuminant) has completely satisfied conditions 1, 2, 3, and 4. Benzine gives a much clearer, stronger, and more uni-

Jan 1, 1886

By David Donoghue

Efforts made in the year 1930 and in previous years restricted production in most of the fields of Texas to a point that was satisfactory, at the beginning of 1931, to the majority of producers and buyers. In the Panhandle, North Texas and West Central Texas districts, a few operators with refinery affiliations or contracts either ignored, or by virtue of injunction suits, did not comply with the Railroad Commission&apos;s orders, and there was some oil sold at less than posted prices, which, with the Oklahoma City difficulties, caused the first general price reduction. More could have been done perhaps to help the situation on the Gulf Coast and in the Laredo district, but natural advantages are not readily surrendered. East Texas Proration troubles in 1930 were insignificant when compared with those of 1931. In January, 1931, efforts were begun to convince the producers and citizens of East Texas of the necessity of curtailment. Opposition quickly developed and meetings were held in the towns of the region and proration denounced vigorously. Notwithstanding a strenuous campaign for additional legislation waged by many producers, the regular session of the State Legislature refused to strengthen the conservation laws and passed only the Marginal Well Bill, designed to prevent the Commission from prorating small wells. The Railroad Commission held a heated hearing on East Texas in the latter part of March. During April the Commission issued three orders based on the Yates plan for the proration of the East Texas field. Each succeeding order raised the allowable for the field. In June the opposition held more mass meetings at which a plan based on acreage was endorsed. Apparently on the theory that any plan was better than none, the Commission issued an order on July 2 embodying some of the features of the proposed plan, limiting production to 250,000 bbl. per day, and dividing the producing area into 20-acre units participating equally in the outlet. Owing to the bringing in of many wells and the many violators of the Commission&apos;s orders, production increased to such an extent that prices went as low as 5c per barrel.

Jan 1, 1932

By R. C. Canby

The difficulty of exact neutralization by ammonia of the acid solution obtained in the determination of arsenic by the method of fusion with carbonate of soda and nitrate of potassium, led me to try the effect of neutralization by oxide of zinc. I obtained most satisfactory results, and found a great saving of time. The oxide of zinc being added in excess, there is no delicate testing with lit? mils paper and tedious alternate adding of dilute ammonia arid acid until the proper point is reached. The excess of oxide of zinc, too, seems to hold, from the filter, the gelatinous silica and alumina, which are usually precipitated upon neutralization, and thus to render the washing of the precipitated arseniate of silver almost invariably much more rapid. Except the substitution of the neutralization by oxide of zinc for the more tedious method by ammonia, the details of the process are practically the same as those published by Mr. Richard Pearce, of Argo, Colorado (Proceedings of the Colorado Scientific Society, vol. i.), who shows what very accurate results can be obtained by the fusion process. I have made numerous tests of comparison between the two methods of neutralization, and find that those by the oxide of zinc agree almost exactly with the old method. Increasing the quantity of nitric acid, even to considerable excess, to be neutralized by the oxide of zinc did not affect the precipitation of arseniate of silver. The process may be outlined as follows : Take 4 to 1 gramme finely pulverized ore, and mix in a porcelain crucible with eight to ten times its weight of a mixture of equal parts of carbonate of soda and nitrate of potassium (Kerl. Metallurgische Probirkunst gives 4 to 5 nitre to 14 soda). Gradually bring to fusion and keep so, three to five minutes. Cool. Disintegrate in hot water. Filter and wash with hot water. Acidify the filtrate with nitric acid, and boil to expel carbonic acid and nitrous fumes. Cool. Add an excess of an emulsion of oxide of zinc. The bottom of the beaker should have quite a layer of oxide of zinc, after stirring.

Jan 1, 1889

Francis Drake, Bulawayo, Rhodesia, So. Africa (communication to the Secretary *):—I should like to place on record some data in addition to those given by Mr. Canby in his paper. I regret that my notes have been destroyed so that I can give no accurate measurements of the water jacket that I am about to describe. This furnace mas erected in Cerro Gordo, Inyo county, Cal., early in 1875, and I think it quite possible that it was the first applied in lead smelting. It was made of plate iron and elliptic in shape, the inner dimensions being about 54 by 42 in. by 48 in. high. The distance between the inner and outer plates was about 6 in. Tuyere holes, one at the back and two on each side, about 12 in. in diameter, were made in this, and in these were placed cast-iron water tuyeres about 16 in. long, the diameter of the blast orifice at the point being about 3 in. The height from tuyeres to feed door was about 9 ft., but the top of the charge was kept about 5 ft. above the tuyeres. There was a space of about 12 in. between the jacket and the top brick-work. This brick-work was supported by a cast-iron plate resting on four cast-iron columns. At the beginning, the jacket was lined with air-dried radial bricks, made of crushed quartz and fire-clay, as it was thought that the jacket would not stand the heat on its bare plates. After a short time the practice was altered and no lining mas put in. The jacket was closed at the top and had a steam drum connected by two pipes at the back. This steam drum was connected to the boiler in which the steam was made for driving the Baker blower, the rock breaker and the pumps. The bottom of the jacket mas also connected to the boiler. The jacket was run under boiler pressure (80 Ib.) for some time, but eventually cracks developed in the inner plate between the tuyere holes,

Jan 1, 1913

By H. W. Camp

In attempting to summarize and pick out the outstanding development,s in refinery engineering during the past 12 or 13 months, one is immediately impressed by the great strides that have taken place. It is, of course, difficult to obtain the proper perspective with the old year so fresh in our minds, and if relatively minor improvements seem to be given equal recognition with those of magnitude, it will be because the nature of the human mind causes us to place the trivial incidents of today with the important things of yesterday. For instance, the Twenly-Second Semiannual Motor Gasoline Survey (December, 1930) of the U. S. Bureau of Mines shows that the total gasoline yield per barrel of crude increased from 39.6 per cent.. in 1929 to 41.99 per cent. in 1930. This latter fact may appear rather confusing since the production of high-gravity crudes has been steadily increasing. However, during the past yew there has been a reduction in gasoline end point of approximately 8" F. which roughly corresponds to about 1.0 per cent. yield from the crude oil. It appears, therefore, that, if the gasoline mere based on a corresponding distillation basis 1930 would show better yields from the crude than 1929. Cracked gasoline increased from 14.83 per cent. in 1929 to 17.46 per cent. in 1930. Percentage of total gasoline from cracking stills has doubled since 192.5, thus indicating the extent to which this phase of refining has advanced over past years. Replacement of the old shell still batteries by a pipe still and single flash system, with an efficient fractionating tower, has proved advantageous both in fuel consumption and in decreasing space required for the installation. Considerable activity has been shown in the field of vapor-phase cracking, with the development of several new types of units. The production of a product with a high antiknock value makes the vapor-phase processes particularly attractive. Cracking equipment has shown a marked advance with the development of corrosion-resisting alloys. Nickel, chromium and vanadium have shown interesting possibilities, but as yet are fairly expensive. Ceramic material for lining reaction

Jan 1, 1931

By R. E. Collins, Paul B. Crawford

Mathematical equations have been derived to show the effect of the slippage phenomomenon (Klinkenberg effect) on unsteady-state gas flow through porous media. The assumption is made that the slippage may be represented by an equation of the type It is pointed out that most of the existing data on unsteady gas flow may be corrected for slippage by a simple change in definition of the dimen-sionless groups. INTRODUCTION Several solutions to the various problems associated with the unsteady-state flow of gas through porous media have been recently presented in the literature.&apos;,&apos;" The cited publications have resented solutions for flow under ideal conditjons. The principal assumptions involved include: (a) the density of the gas obeys the perfect gas law; (b) the viscosity of the gas is constant; and (c) the gas permeability is constant. Few, if any, actual gases under reservoir conditions are believed to conform with the above, but the ideal solutions do provide the basis for making improved estimates on the performance of gas reservoirs. The purpose of this paper is to show the performance characteristics when assumption (c) is corrected for the slippage phenomenon or the Klinkenberg effect. This is believed to be a step nearer to reality. MATHEMATICAL DEVELOPMENT Case 1. Gas Flow — Ideal Conditions The equations describing the flow of gas under ideal conditions have been clearly presented in the cited literature; however, for completeness of this work they are repeated here. The basic differential equation describing the flow of gas is Equation (6). It may be derived as follows: The continuity equation, the perfect gas law and Darcy&apos;s law are combined to give: Manuscript received in the Petroleum Branch office Aug. 3, 1963 or If — is constant, Equation (5) is rewritten to form the basic Equation (6). or for the linear case A dimensionless equation is obtained by dividing through by (pl)z and making the substitutions shown below: The resulting equation is A similar procedure for the radial case leads to the following equations: where and Equations (11), (12), and (13) are those used by Bruce, et al., and Jenkins and Aronofsky for their computational work.

Jan 1, 1953