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By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;' Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of' the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.' In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By F. G. Miller, R. C. McFarlane, T. D. Mueller

During the process of gas storage in pressure-depleted oil reservoirs, it has been observed that in some instances additional liquid oil is recovered and that the composition of the storage gas is materially altered. A mathematical study was made of the dynamic behavior of such a depleted oil reservoir undergoing gas injection. The important variable considered in this study, not included in previously published work, was that of compositional effects on the phase behavior of two-phase flow. Pressure, saturation and component composition profiles were developed for a linear, horizontal and homogeneous porous medium containing oil and gas but undergoing dry gas injection. Special new techniques were developed to overcome the problems of numerical smoothing which arise in the solution of the equations representing such systems. The method of solution includes the development of partial differential equations describing the behavior of the system, representing these equations by finite difference approximations, making certain simplifying assumptions and, finally, applying methods of numerical analysis with the aid of a high-speed digital computer. In an example calculation, results using the mathematical model are compared with field observations made on a gas storage project in Clay County, Tex. This field project involved a depleted oil reservoir used 'for gas storage and gas cycling purposes. As a result of these processes, the reservoir yielded substantial amounts of secondary oil, both in the form of stock tank oil and as vaporized products in the produced gas. The methods derived in this study may be applied to a variety of oil reservoir problems which are dependent on compositional effects. In recent years the number of oil reservoirs being used for gas storage purposes has increased greatly, and there has been at least one published account of additional oil recovery resulting from gas cycling a depleted oil reservoir after repressur-ing with dry gas for storage purposes. Additional oil recovery from oil reservoirs resulting from gas storage operations could become an important secondary recovery process. This is especially true since the use of natural gas in large metropolitan areas continues to increase and more gas storage volume near these areas is needed. These facts provided the motivation for the work reported here. This paper reports on a study of the inter-relations of composition, saturation and pressure changes which occur when hydrocarbon gas is injected into an oil reservoir system. From an understanding of the process, prediction methods may be developed for use in forecasting the secondary recovery products from gas storage operations in oil reservoirs and, consequently, .the economics of such projects can be developed. The process of storing hydrocarbon gas in an oil reservoir and the cycling process both involve the transient multi-phase flow of oil reservoir fluids with changing fluid compositions. There is a scarcity of work published on the subject. One of the first laboratory models developed to study a problem similar to the one posed here was published in 1948 by Standing, Lindblad and Parsons. l They developed a model to study gas condensate recovery by gas cycling, including the effect of heterogeneous reservoir permeability. Their results showed the compositional effects of injecting a gas of known composition into a two-phase condensate reservoir of known composition. A major finding of their study indicated that maximum oil recoveries from gas cycling projects result when low cycling pressures are used. Previous to their work it was generally considered

By W. A. Tiller, S. O’Hara

Grain refinement in stirred melts has previously been shown to arise from dendrite segmentation. The present work discusses experiments capable of distinguishing between remelting and mechanical effects which result from fluid motion. Nucleation of still un-dercooled Sn-1 pct Pb melts with a single-crystal seed shows that the grain size of the resulting ingots decreases as the undercooling at nucleation increases up to about 1Z0C, then increases again for larger undercoolings. Pure melts exhibit little refinement as a result of nucleation at any undercooling up to 12°C. The presence of fluid motion gives rise to grain multiplication in pure melts, but the magnitude of this effect is partly obscured by solid-state pain growth. The results indicate that two grain-multiplication pvocesses can operate, one which involves dendrite remelt ing, and another associated with fluid motion. Small ingot experiments indicated that an equiaxed transition can be caused by fluid motion. THE presence of forced convection during recales-cence of undercooled Sn-1.3 pct Pb melts has been shown to give rise to extensive grain refinement during solidification of small ingots of this alloy.''2 In Ref. 2, this refining was shown to result entirely from dendrite fragmentation and not from any nucleation mechanism. The purpose of the present work is to establish what processes lead to dendrite segmentation. Experiments were therefore carried out to determine the resulting structure of both pure tin and Sn-1 pct Pb melts, nucleated at various undercoolings by single-crystal seeds in the absence of forced or natural convection. By comparing the information obtained from these experiments with the results of Refs. 1 and 2, the effects of fluid motion on the ingot structure, and the details of the segmentation mechanisms, should become clear. The results of these experiments should also be helpful in understanding the solidification structures of larger ingots since natural convection, which is known to play an important role in determining ingot structure13 differs only in degree from the fluid-motion effects studied here. I) EXPERIMENTAL PROCEDURE The apparatus shown in Fig. 1 was constructed to permit controlled nucleation of stirred or unstirred supercooled melts using a seed oriented in the tin dendrite growth direction. Because the melts, in all cases, were capable of larger supercoolings than the one used in each experiment, the structure observed always resulted from a single nucleation event at the surface. The sequential procedure was as follows: Tin was melted under purified hydrogen and the oxide removed at a temperature of 450°C . Electromagnetic stirring was then used to clear the surface completely and during this time the guide tube was lowered underneath the melt surface. A pointed Czochralski-like crystal was then propagated from a specially prepared tin dendrite seed4 inside the guide tube while the temperature of the bulk melt was held just above the melting point, ensuring a perfectly clean seed which was epitaxial with the original dendrite. The dendrite and epitaxial seed, still in the guide tube, were withdrawn from the melt which, in turn, was undercooled to 2C° below the temperature at which the nucleation experiment was to be performed. The melt was held there for several minutes, both in stirred and in still-melt experiments. The temperature was next raised to the required value and the melt nucleated by the carrot seed inside the guide tube, the heater power being shut off just after nucleation. In experiments where quenching after nucleation was required, a high-density graphite crucible was used, but otherwise the procedure was as described above. The temperature gradient in the melt before nucleation was kept below 1C° per cm by carrying the experiment out just below the center of the heater shown in Fig. 1.

Jan 1, 1968

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By J. A. Holmes

It is a fact that is coming to be more widely recognized by the general public, as well as by members of the medical fraternity, that the health of persons living in our hill-country depends in no small degree upon the drinking water obtained, just as it has been found that the* use of pure water in the lowlands and swamp-areas of the Southern States results in practical immunity from malarial diseases. Hence the problem, how to obtain supplies of wholesome water for the towns and manufacturing establishments in the hill-country or Piedmont plateau-region of the Southeastern States, becomes one of considerable interest, the importance of which will continue to increase, as the favorable conditions for manufactures and agriculture in this region will make it, in the near future, the most thickly populated portion of the South Atlantic States. Water-supplies from Surface-streams are unquestionably of the first importance; and in the mountain counties, where the region is still largely forest-covered and the streams are swift and continually aerated by rapids and cascades, the water is of superior purity and clearness. This statement is also applicable to the more elevated and sparsely settled portions of the Piedmont plateau; but in the less hilly and more thickly settled portions of this region the streams are more sluggish, and the waters more muddy and less pure, owing to the fact that a much larger proportion of the surface is under cultivation.

Jan 1, 1896

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By George S. Rice

A problem of possible subsidence of the surface from mining operations, which might have had disastrous results, arose in 1913 at the Brier Hill mine, of the Penn Iron Mining Co., near Norway, Mich., now managed by Pickands, Mather & Co. for the Bethlehem Steel Co. A double track and sidings of the Chicago & North Western Railroad passed over part of the mine, and if subsidence had reached the surface it might have affected the stability of the tracks. The chief purpose of this paper is to record the facts disclosed by investigations of underground movement from 1913 to 1919, when the tracks were moved, and subsequently at intervals, as engineering data of value from mining carried on below the tracks in the steeply pitching lenses. A secondary purpose of this paper is to describe a novel method for determining the rate of speed of upward breaking above the mine excavations. This method was found effective and might be used elsewhere under similar conditions. The mine workings under consideration were developed from the Brier Hill shaft, which was circular, concrete-lined, 14 ft. in diameter and about 900 ft. deep. They extended about 800 ft. westward from the shaft, and nearly parallel to a corresponding length of the railroad tracks. The highest part of these workings was at a depth of 400 ft. below the tracks (Figs. 1 to 12). The mining company had the right to remove the ore, the railroad assuming that the surface would be supported. Finally, without legal controversy, an amicable adjustment was reached as to what should be done to lessen or obviate the hazard of subsidence. Method oF Mining Before the problem became acute, the mining company, to decrease the possibility of subsidence, had been mining the part of the orebody that lay under the tracks by a room-and-pillar system, back-filling with

Jan 1, 1934

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By E. T. Wessel

UNEXPECTED brittle failures of metals in practical applications are a serious problem to many industries and to the nation as a whole. Considerable effort has been devoted to studies of the brittle behavior in metals. However, the major portion of this effort has been directed at developing techniques and apparatus for the purposes of determining the susceptibility of metals to brittle failure and of making various types of observations of the phenomena. Relatively minor effort has been made to understand the basic mechanisms involved in initiating brittle failures. A more complete understanding of the nature and mechanism of the brittle failure problem would be very helpful in efforts directed toward predicting and avoiding brittle failure and toward the development of suitable materials and designs that are not susceptible to a brittle behavior. The intent of the present investigation is to acquire this basic understanding. The pronounced transition from a ductile-to-brittle behavior is most prevalent in metals having the body-centered-cubic lattice structure, primarily be- cause metals of this structure exhibit a strong dependence of yield strength upon temperature and the rate of straining. The generally recognized qualitative concept of the ductile-to-brittle transition is that brittle (cleavage) failure occurs when the yield strength exceeds the cleavage fracture strength. This condition can apparently be achieved by decreasing temperature or increasing strain rate. Likewise, a normally ductile metal can be made to fracture in an apparently brittle manner by the introduction of triaxial stresses (notches) where the ratio of normal to shear stresses can be increased to such an extent that the normal stress exceeds the fracture strength before the critical shear stress for plastic flow is achieved. Neither of these concepts require any prior plastic deformation or explain why the observed fracture strengths are so much less than the theoretical cohesive strength. The results of several investigations of the ductile-to-brittle transition in body-centered-cubic metals illustrate rather conclusively that measurable amounts of nonelastic deformation do precede cleavage fracture, even at extremely low temperatures. These studies suggested that the early stages of plastic flow, particularly abrupt yielding, and their relationship to brittle fracture should be examined

Jan 1, 1958

By K. Huessener

INTRODUCTION THIS paper attempts a survey of the principles involved in the com¬bustion of blast-furnace gas in boilers and stoves. I do not expect to be able to give much information which is actually new, since the laws and methods of calculation pertaining to this problem are contained in a number of handbooks; but, so far as I am aware, they have nowhere been treated exclusively with reference to this one problem of gas economy. The road which I follow is less that of strictly scientific research than that of the practical engineer, faced by operation problems which require a. quick solution by easily accessible means without a prolonged search in scientific handbooks. For this purpose I give a number of tables and diagrams, as well as the results of many years' practical working experience as combustion engineer, which I trust will prove useful to my readers. HISTORICAL Considering the tremendous efforts made during the last 15 years to increase the efficiency of all kinds of power plants, it is highly surprising that until a comparatively very recent period, progress in the economical combustion of blast-furnace gas has been so slow. The explanation generally put forth, that fuel has been so cheap that it was hardly worth while to bother about this economy, will not hold good, for the greatest trouble was taken to improve the combustion of coal and to reduce the consumption of steam. The most plausible explanation appears to be the general impression, held as an accepted fact, that gas, especially hot, uncleaned, blast-furnace gas, was not a good boiler fuel. Many managers of high repute had tried unsuccessfully to improve the conditions of its use, and the dictum went forth that efficiencies of over 60 per cent., particularly with high loads, were impossible. This was the situation not only in the United States, with very cheap fuel, but also in Europe, where fuel prices are twice and three times as high.

Jan 2, 1916

By C. Fairhurst, A. M. Starfield

As a practicing mining engineer, I face many rock mechanics' problems daily and would like to mention one or two examples to illustrate the current gap between laboratory investigations and actual field problems. I would like to endorse Dr. Obert's suggestion that more field measurements and observations should be undertaken. There is an ever-increasing body of data beginning with Hast's results in Sweden,l then measurements at Elliot Lake, Canada, and so on, including our own measurements at White Pine, which clearly indicate that the horizontal stresses underground are often at least as large as the vertical stresses. Visual obsenation of the deformation of roof and pillars (including failure due to horizontal compression) also demonstrates that the horizontal stresses are often most important. Yet almost every laboratory investigation begins with the assumption that the only stresses acting are vertical. Roof spans in layered formations. for example, are calculated on the assumption that the rock behaves as a gravity loaded beam. This is all too often unrealistic. Roof bolts are also often considered to be simply means of suspending the gravity loaded beams. As Dr. Reed has mentioned they are probably, in fact, acting to restrain a beam which is attempting to buckle due to lateral pressure. The fact that moisture can reduce the strengths of some rocks as much as 50 percent has been known for many years. In the mine me are almost always faced with wet rock, yet no one has investigated ways in which this wakening effect can be overcome. as, for example, by waterproofing the rock. C. Fairhurst, University of Minnesota I would like to mention that we have found,2 from stress-relief determinations, that appreciable (over 1000 lb per sq in.) horizontal pressures occur also at the surface in granites quarried in central Minnesota. Whilst I agree that more field measurements are desirable, it is important to point out that most university research is undertaken by graduate students who must attend classes daily. Their research is therefore restricted to the laboratory. A.M. Starfield, University of Minnesota No one denies the importance of obtaining: data from field measurements. It is equally important, however, that field measurements be guided by theory. Much time and money can be wasted by indiscriminate measurement. An example of the value of theory in interpreting measurements is given in Dr. Obert's comments on the time dependent strain observed in a salt mine. He anticipated that the stress at the wall of the opening would change with time because salt is viscoelastic rather than elastic. It can be shown from theory that if an excavation in a viscoelastic medium is unsupported, then the stress at the wall does

Jan 1, 1967

By E. W. McAllister

The decision of the California Oil Umpire's' office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in thcir respective wells. Shortly therefter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clark and C. B. Kimberlint in a report2 dated March 1933. PRODUCTIVITY Index In the majority of individual well problems involving the use of subsurface- pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettlcman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time fur various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

By E. W. McAllister

The decision of the California Oil Umpire's' office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in thcir respective wells. Shortly therefter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clark and C. B. Kimberlint in a report2 dated March 1933. PRODUCTIVITY Index In the majority of individual well problems involving the use of subsurface- pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettlcman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time fur various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

By Van Dyne Howbert, Fred E. Gray

The Presidio mine of The American Metal Co. of Texas is situated 45 miles south of Marfa, Texas, a town on the Southern Pacific R. R., and lies approximately 20 miles north of the Mexican border. Communication with the railroad is maintained over a state highway. All supplies for mine and mill are hauled in by truck from Marfa and precipitates and concentrates are freighted to the railroad by the same means and shipped to Selby and El Paso, respectively. The mill is at the town of Shafter, 1 mile from the mine and at approximately 350 ft. lower elevation. The ore is conveyed to it by an aerial tramway which requires practically no power on account of the difference in elevation. The mill is a countercurrent decantation cyanide and gravity concentrating plant of 200 tons daily capacity. Coarse and fine crushing are done at the mill. Two neal-by shallow wells in the bed of Cibolo Creek furnish an abundance of water. Power is generated for the mill and town by a Diesel engine plant. Ore Treated The ore is oxidized and siliceous. The greater part contains approximately 16 oz. of silver per ton, but mixed with this are many particles of ore of much higher grade, assaying in many instances 100 oz. or more. In the 16-oz. material there is an almost constant amount of silver which is difficult to recover by cyanidation. The high-grade material contains a much greater proportion of silver which is easily amenable to cyanide treatment. Thus, as the grade of ore becomes higher, the percentage of recovery of silver increases rapidly, under equal milling conditions. The silver minerals contained in the ore are principally argentite and cerargyrite, the former predominating The lead minerals, all of which are argentiferous, are chiefly cerussite and galena, with occasionally a little anglesite. The gold is free; most of the ore contains merely a trace

Jan 1, 1935

By S. V. Krishnan, I. Iwasaki

In the upgrading of finely disseminated iron ores, selective desliming is the critical step that must be controlled to achieve efficient flotation. A prerequisite for selective desliming is a properly-dispersed pulp; sodium silicate is commonly used as a dispersant. The mechanism by which sodium silicate acts as a dispersant in the presence of calcium ions was examined by streaming potential measurements, settling tests, abstraction density determinations, selective flocculation tests, and scanning electron microscope observations. The study established that calcium silicate precipitates on the mineral surfaces dispersed the pulp. Although sodium silicate was a nonselective dispersant, the addition of corn starch aided flocculation of goethite over quartz at low silicate additions, but became ineffective at higher silicate levels. A model is presented to explain the dispersant mechanism of sodium silicate in the presence of calcium ion for selective flocculation of iron ores.

Jan 1, 1983

By Walter B. M. Davidson

Phosphorus is one of the elements having the widest distribu tion, and phosphoric acid plays an important part in the composition of the crust of the earth. It is allied in various chemical combina- tions with many bases, of which lime, alumina and iron are the most common. It is difficult to state in what chemical combination phosphoric acid predominates in the crust of the earth, for while phosphate of lime, as the mineral which is sought for and found in deposits of economic value is the most familiar, it is probable that the phosphates of alumina and iron are the most usual forms in which phosphoric acid exists in all soils not essentially calcareous. It has been shown by thousands of analyses that all fertile soils contain from a trace to 0.5 per cent. of phosphoric acid. All limestones, dolomites and chalks contain it in proportions which, though usually small, are large enough to make careful analysis necessary in the selection of limestone as flux for iron-smelting. It is generally Trenton limestones that are found best for this purpose, the more recent strata being more phosphatic. In some places phosphoric acid replaces carbonic acid, and the limestone or chalk becomes phos phatic to a large degree, or sometimes pure phosphate of lime. The waters of the ocean, from very early periods, have contained phosphoric acid. Different analyses show varying contents; it is asserted that some portions of the Gulf Stream are more phos phatic than the surrounding waters of the Atlantic. Many springs, usually from limestone regions, contain soluble phosphates in vary ing quantities. I think it safe to assert that phosphorus is nearly the most widely and evenly distributed element on the surface of the earth, and probably the most subdivided. This can be readily understood when the important part which phosphoric acid plays and has played in the vital cosmos is taken into consideration. Phosphorus was on the earth in gaseous, liquid or solid form before the dawn of life, and since then all animal and vegetable creation have combined with the

Jan 1, 1893

By T. L. McCall

This is a continuation of the paper on bumps presented by the late Mr. Herd in February, 1929. The seam worked consists of bituminous coal, 9 ft. thick, pitching 20°, and now under a depth of cover of 2800 to 3200 ft. Full particulars are given of two bumps that happened in November, 1931, with an interval of only 9 hr. between them. The first was a "district" bump affecting an area of 1000 ft. on the strike by 700 ft. on the dip and rise, beginning at a distance of 1000 ft. from the long-wall faces. The second, which caused much greater damage, was localized to two levels 200 ft. apart, in the area left undisturbed by the first bump next to the longwall faces. Observation stations had been established in the workings in 1931 and definite records were obtained on the flow of coal taking place from the edge of large pillars developed for retreating work, into the open roadways. The records also gave evidence that "advance weighting" or "underdraw " was affecting the coal at an average distance of 260 ft. in advance of the longwall faces. The author propounds the theory that the sandstone bed varying from 0 to 75 ft. in thickness and lying 14 ft. above the coal acts as a slab in distributing the superincumbent weight. The weight is thereby concentrated on the pillars in advance of the longwall faces and this load, in conjunction with a pavement strong enough to resist the reaction, leads to overstressing the pillars, which finally collapse suddenly, thus giving rise to this particular type of low side bump. The overlying sandstone bed, which is apparently a condition common to all coal mines in which bumps occur, is not necessarily a massive bed, as the thickness of this bed at Springhill in the area that has experienced these severe low side bumps is only 25 to 31 feet. A list of 43 minor bumps occurring in the past 2½ years is appended

Jan 1, 1934

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution.

Jan 9, 1950

By H. Reinhardt, P. Haglund, J. Rydberg, B. Lunden

As legislation to minimize pollution in effluent streams becomes stricter, it is important to treat used acid pickling baths before discharge. This is usually achieved by neutralization of the acids and precipitation of the dissolved metals in such a way that neither acids nor metals can be re-used. A process has been designed and tested on a pilot plant scale to recover both acids and metals from a stainless steel pickling bath leaving only Na2SOs in the effluent. In this process, H2SOr is added to the spent pickling liquor and the recovery of the pickling acids HN03 and HF is achieved by solvent extraction, using TBP in kerosene as the organic solvent. The extracted acids are stripped with water, giving an acid concentration high enough for direct use in the pickling bath. Molybdenum is also extracted by TBP and is recovered in a separate step. The other metals, Fe, Cr and Ni, are precipitated from the raffinate as hydroxides, dried and recycled to the metal process. In evaluating this process, comparative experiments with mixer-settler and pulsed column have been performed. The process described is being considered for use by a Swedish company pickling 70,000 tons per annum of stainless steel.

Jan 1, 1973