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US 4,190,434 - In the thermal production of magnesium metal, a mixture of calcined dolomite, an iron- silicon-aluminum alloy as a reductant, and residual slag from the production of ferrochromium is smelted to evolve magnesium vapor, which is then condensed. The use of bauxite is lessened or eliminated because of the relatively high alumina content of the residual slag. R. Bonfils, A. Mena, C. Payn, and L. Septier, assigned to Ste. Francaise d’Electrometallurgie (SOFREM). Feb. 26, 1980. 6 pp. (75-10R). Filed: 6-14-78 (915,387). Priority: France, 6-24-77 (77/20,227).

Jan 1, 1982

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By Louis A. Panek

The purpose of this paper is to present a method of designing safe and economical arch structures that are to be constructed of concrete or directly of original earth materials. The experimental data used to illustrate the design method are taken from Bucky and Fen tress,1,2 and the application of the ideas presented by them is extended by obtaining an additional set of curves from which arch structures may be designed. This design method is based upon the following principles of similitude: A scalar model made of the same material as that of the full sized structure will behave similarly to its prototype if the density of the model is increased in the same proportion as its linear scale is decreased. Let R represent the scale or model ratio, namely, the ratio of a prototype linear dimension to the corresponding model linear dimension. The effect of increased density may be obtained by rotating the model in a centrifuge at a speed such that the centrifugal held exerts on the model an accelerative force R times the accelerative force of gravity. Under these conditions; (I) model unit stresses are equal to corresponding prototype unit stresses, (2) the ratio of the prototype deformation at a given point to the model deformation at a similar point is equal to the scale ratio, R, and (3) the model and the prototype will behave similarly within and beyond the elastic limits of strain. According to the above relations, such models can be used to solve the following problems: I. The dimensions of the most economical safe arch structure for a given load. 2. The miaximum safe roof span underground for given geologic conditions. The procedure is described briefly as follows. Tests are made by rotating in a centrifuge a number of models that repiesent a variety of prototype loads and dimensions. From the experimental data, curves are plotted to show the relations between these loads and dimensions. The curves are used to solve directly the problems stated above. Structural design is based upon the working (safe) stress of the material of construction, which is established by applying a factor of safety to the experimentally determined ultimate strength of the material. In conformity with this principle, each model is gradually loaded until failure occurs. A safety factor is then applied to the results. If a safety factor of 4 is used, a given model at failure represents a safe prototype, the linear dimensions of which are equal to one-fourth the model ratio at failure times the corresponding model dimensions. The safe model ratio is computed from the following formula: Safe R =(1/4)4p2n2r/g=p2n2r/g [I] in which: n = centrifuge revolutions per second at model failure; r = radius of rotation of the model in feet; g = 32.2 ft/sec2.

Jan 1, 1949

LOUIS Buchman walks down the hall of Kennecott's Chrysler Building offices as if he belonged there, but it wasn't his setting of choice. The West has become his home, that and the scene of operations is there. When he was a child his family came to the United States from Latvia and settled in Michigan's Upper Peninsula where he went to school and on to Michigan College of Mines. Graduating with B.S. and E.M. degrees, he headed west in 1907 to the mining camp of Ophir, in the state where he spent the bulk of his career - Utah.

Jan 5, 1953

By C. S. Matthews, M. Prats, R. I. Jewett, J. D. Baker

By mathematical analysis it was found that injectivity history of a uniform five-spot pattern can be calculated by rather simple formulas. These calculated injectivities were found to agree rather well with injec-tivities measured in a potentiometric analog. With this as a basis, a simple method was finally developed which allows prediction not only of rate of injection but also of rate and kind of production at the production well, for a uniform five-spot. Using this method formulas for the eflective injectivity and production behavior of a waterflooded reservoir having a wide range in permeability can be calculated by considering that the reservoir consists of several layers, each having a uniform but different permeability. Rather good agreement is shown by a comparison of the observed production history of a field in the Illinois basin and that calculated by the methods just described. INTRODUCTION The importance of being able to predict the injection rates for a water flood is well known, for upon injection rate depends the life of the flood, the size of pumping and treating facilities, and the rate of oil recovery. One method of determining rates of injection is through a pilot flood. However, it appears that even if a pilot flood is resorted to, a theoretical method for calculating injection rate will be valuable in extending field results to times after inter- ference and to locations of other five-spots. It is also important to be able to predict the production history of a flood. Such prediction must generally be done by theoretical means, since in general a small pilot flood will not furnish much quantitative information in this regard because of the distortion after oil-bank interference. Methods for predicting the behavior of five-spot water floods have been proposed by Yuster and Cal-houn' and by Hurst.? However, these methods do not consider the effect of the mobility of the different fluids in the reservoir. Other investigators3,4,5,6 have determined the effect of the water-to-oil mobility ratio on the production history by means of different experimental techniques. Most of the published work applies to homogeneous sand bodies, does not provide information for determining the injection requirements of a flood, and seldom considers the rate of build-up of the oil bank as it fills up the partially depleted reservoir.* The present work was undertaken because of the lack of predictive method which takes into account mobility ratio and the rate of buildup of oil bank resulting from the void space in a partially depleted reservoir. As water is injected into the reservoir, which contains oil, water, and gas in macroscopically homogeneous saturation, it forms several banks ahead of the injection well. In each bank or region there is assumed to be only one mobile phase—water in the water bank, oil in the oil bank and gas in the gas region. The saturation in each region and a plan view of the banks are shown in Figs. 1 and 4, respectively. FACTORS AFFECTING INJECTION AND PRODUCTION RATES Results in this report are determined as functions of the three parameters, F, M, and M, , and of a fourth parameter, r,/L** which relates the size of the well to the flood spacing. The parameter F is the displacement factor defined by Hurst in Ref. 2. It determines the rate of build-up of oil bank as it fills up the partially depleted reservoir. When gravity effects are neglected, the four parameters just given are sufficient to describe the waterflood behavior for horizontal and homogeneous reservoirs having incompressible liquids. Definition of InjectIvity The dinlensionless injectivity (or injection rate) used in this report is defined by

By R. E. Mussler, F. E. Block, T. T. Campbell

An exploratovy study was made to deternzine the feasibility of preparing beryllium by the metallother-. mic reduction of beryllium oxide. The procedure involved heating a relatively nonvolatile metal reductant in contact with beryllium oxide in a vacuum. Beryllium vapors formed in the reaction were condensed as a coherent deposit on a heated surface. Reductants tested included tanthanun, yttrium, thorium, Th-Mg, and Zr- Ti alloys, and the hydrides of lanthaniir~z, yttriunz, and zirconiur?7,. Test ten7pevatures ranged from 1350'to 175O' C, and reaction times ranged frot 30 to 100 lzr. In most cases metal recoveries were lola, although yields close to 90 pct of theoretical were obtained with latzthanum, yttrium, and zirconium reductants. In most cases metal deposits were contanzinated by beryllides, /ls/cally of the Beln M or Bel3 M type. BERYLLIUM has a variety of unique properties including light weight (sp gr 1.85), low thermal neutron absorption cross section, high scattering cross section, excellent dimensional stability, high strength to weight ratio, high melting point (1285"C), high specific heat, and high thermal conductivity. Interest in beryllium as a structural material in aerospace and nuclear-reactor applications is based on these properties. In general, the potential of beryllium has been only partially realized, largely because of the brittleness of poly crystalline forms of beryllium, difficulties associated in its fabrication, and joining problems encountered in its use in structural applications. Several excellent books and monographs are available to those interested in the occurrence, extractive metallurgy, and utilization of beryllium.1"* Although an extensive amount of research on beryllium has been in progress during the past 10 years, much of the work has been concerned either with the so-called "ductility problem" or with the development of methods of fabrication and evaluation of properties of various commercial or purified grades of metal. A recent survey of the literature indicates that only limited efforts are presently being directed toward developing new methods for reducing beryllium compounds to metal. Two major commercial methods now used to produce beryllium are the magnesium reduction of beryllium fluoride and e lec trow inn ing of beryllium from fused sodium chloride-beryllium chloride salt baths. Only a limited amount of work has been done on the direct reduction of beryllium oxide. Major factors which complicate this method are the great stability of beryllium oxide and the reactive nature of beryllium metal. The stability of the oxide necessitates extremely high reduction temperatures and vacuum operation to liberate beryllium metal vapor and cause reactions of the following type to proceed: XBeO(s) +YM(s)-MYOX(s) + XBe(& As early as 1939, roll' used this reaction for the direct reduction of beryllia by zirconium and titanium, and later in 1952 ~a~el~ studied the reduction of beryl-

Jan 1, 1967

By R. F. Hehemann, R. H. Goodenow

Thermal arrest, hot-stage microscopy, and transtnission electron microscopy techniques have been employed to study the transformations in low-carbon iron and Fe-9 pct Ni alloys. In continuous cooling experiments, each alloy transforms at an essentially constant temperature for cooling rates below the critical rate required for martensite formation. However, high-tenzperature transformation in pure iron takes place by a different mechanism than that in the 9 pct Ni alloys. Pure iron exhibits an equi-a a structure with a low and random dislocation density while the 9 pct Ni alloy exhibits a cell or lathlike substructure analogous to that of low-carbon martensite. This same substructure characterizes upper bainite in higher-carbon inaterials. UNTIL relatively recently, diffusionless transformations have been considered to take place by the same mechanism and have been termed mar-tensitic transformations.l-3 The most characteristic feature2 of this mode of transformation is the shape change produced by a shear deformation and growth of the product phase frequently occurs at an extremely high velocity approaching that of an elastic wave.4'5 A different mechanism of diffusionless transformation was recognized first in Cu-Ga and other copper-base alloys.6,7 From the absence of surface tilting in these alloys, it has been concluded that transformation is not accomplished by the cooperative shear displacements that occur in mar-tensitic reactions. Transformation presumably takes place by the rapid movement of an incoherent interface which is capable of propagating across parent grain boundaries. Although the transformation is diffusionless in the macroscopic sense, advancement of these interfaces is accomplished by an atom by atom rearrangement. Transformations of this type therefore require thermal activation and are generally operative only at high temperature. Although requiring short-range diffusion at the interface, propagation still occurs so rapidly that the reaction cannot be suppressed with normal cooling rates.7 The resulting microstructures exhibit large, irregular-shaped regions of the product phase, which are essentially free of crystallographic features. Consequently, these reactions have been termed massive transformations. Transformation by the massive mechanism has been reported to occur in ferrous systems involving pure iron and binary alloys of iron with nickel, chromium, and silicon by Gilbert and owen.' The Fe-Ni system is of special interest in that the massive transformation was observed in alloys with less than 15 pct Ni while alloys having more than about 28 pct Ni transformed by the conventional mar-tensitic mechanism. By employing cooling rates substantially higher than those used by Gilbert and Owen, Swanson and Parr have been able to suppress the massive transformation in alloys with 0 to 10 pct Ni9 and produce martensite as revealed by surface relief. The massive transformation in the alloys having less than 15 pct Ni was identified by the lack of surface relief and an irregular rather than clearly acicular microstructure.' Speich and Swann, using thin-foil electron microscopy, identified three distinctly different structures10 in quenched binary Fe-Ni alloys. From 0 to 4 pct Ni the structure consisted of blocky grains of a with a low and random dislocation density. Alloys with 4 to 25 pct Ni exhibited a cell structure with a high dislocation density; and at greater than 25 pct Ni the structure consisted of internally twinned plates. The structural change at approximately 4 pct Ni suggests that alloys with low nickel content transform by a different mechanism than those with intermediate nickel contents and the transition from the cellular to the internally twinned structures at approximately 25 pct Ni is analogous to the transition from needles to internally twinned plates that occurs over a narrow range of carbon contents in Fe-C martensites.11,12 Conventional bainitic and martensitic modes of austenite decomposition operate in ternary Fe-C-Ni alloys having less than 10 pct Ni. This investigation was conducted in order to explore the conditions under which the massive, bainitic, and martensitic transformations occur and the relationships between these modes of decomposition.

Jan 1, 1965

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By John Dasher

Chemical processing is descended from alchemy, which developed our major lixivants. The profession might have done more if it had been less preoccupied with turning base metals into gold-a process that still hasn't been developed. Georg Agricola, over 400 years ago, gave us ten recipes for "aqua valens" to part gold and silver, and described cementation of gold and silver on base metals. His text stood for 200 years, by which time heap roasting, leaching and cementation were winning copper from pyrites at Rio Tinto and the Barba furnace was distilling mercury from the ores of Almaden.

Jan 1, 1971

By Morris Cohen, Robert C. Ruhl

Fe-Ni-B alloys were inresligated by X-ray diffraclion after splat quenching. Although this rapid cooling did not produce a measurable supersaturation of dissol1ed boron in either binary Fe-B or Ni-B alloys, a marked increase in dissolved boron was achieved by the splal quenching of lernary Fe-Ni-B alloys. Boron additions up to 2.0 wl pcl to Fe-13Ni and Fe-24Ni alloys cause an increase in retained austenite from 0 to 59 pet and to 92 pet, respectively. The martensitic phase in the Fe-13Ni-9 at. pct B alloy is .found to conlain about 0.6 at. pet interstitial boron, as evidenced by the tetragonality of this phase, and about 3.6 at. pct substilutional boron, us deduced from the lattice paratrieler decrease, the balance of the boron being precipitated as (Fe,Ni)aR. The austenitic Fe-Ni-B plznses also contain both interstitial and substitutional boron. Iron-Boron System. The phase diagram and related information about the solid solutions and intermediate phases in the Fe-B system are given by ansen,' Elliott.2 and Pearson.1 The equilibrium solid solubility of boron in both ferrite and austenite is quite small: the maximum solid solubility of 0.02 wt pct B (0.11 at. pct B) occurs in iron at the eutectic temperature of 1150°C. while the maximum solubility in a iron is less than 0.01 wt pct.l There is disagreement in the literature as to whether these solid solutions are substitutional or interstitial. Based on the measured activation energy of boron diffusion in iron, it appears likely that boron moves interstitially in austenite. 4 However, this observation does not rule out the possibility that some of the dissolved boron may also occupy substitutional sites in this phase. Investigations of internal friction of boron in iron have suggested that boron is interstitial there.' Shevelev, 5 on the other hand, reports a decrease in the ferrite lattice parameter with dissolved boron content, thus indicating a substitutional solution. Unfortunately. Shevelev's methods and analysis are unclear. Goldhoff and spretnak6 have measured the lattice parameters of pure iron and an Fe-0.005 wt pct B (0.027 at. pct) alloy at both room temperature (ferrite) and from 920° to 1200°C (austenite). They reporte: a lattice contraction in the ferrite of 0.0003 ± 0.0002 due to boron, thus indicating a predominately substitutional solution. Appreciable (0.0010 to 0.0060) lattice contractions were found in boron-containing austenites, but these effects were much larger than could be accounted for by the substitutional solution of all the boron present. Nickel-Boron System. Elliott 2 gives a summary of thephase diagram and recent work on this system. The solubility of boron in nickel reaches a maximum of 0.03 wt pct at the eutectic temperature of 1080°C. Iron-Nickel System. ansen' presents the equilibrium diagram for this system and also discusses the metastable austenitic and martensitic phases along with the a=? transformations. The lattice parameters of Fe-Ni ferrites have been recently redetermined by Abrahamson and Lopata.7 Their data, Fig. 1, show an unusual change in slope at about 1.7 at. pct Ni. Very few measurements of the lattice parameters of Fe-Ni martensites are available in the literature. The values of Roberts and Owen8 are considerably higher than those measured in the course of the present work: they find that a, is constant at 2.874? from 8 to 30 at. pct Ni. Both the slope change in the ferrite parameters and the occurrence of a maximum plateau in the marten-sitic lattice parameters vs composition denote the

Jan 1, 1970

By Marie Kinzel

LOS ALAMOS, New Mexico, the birthplace f the atomic bomb, is one of the most famous-and mysterious-places in the world. It leaped into fame on Aug. 6, 1945, when the first atomic bomb burst over Hiroshima. Unheard of until that day, its present life is as hidden from most people as was its very existence in pre-Hiroshima days. Then, those who did know of it dared not breathe their knowledge. "What do you tell your wife when you go to Shangri La?" was the favorite quip of the few consultants who made regular trips from east or west to Los Alamos during the tense months when the bomb was in the making. Security regulations made it impossible even to hint at the rigid secrecy surrounding the project. The puzzled wives in question knew only that their husbands had top priority on airplane flights to Albuquerque. When they had verified the safe arrival of the flight, they undoubtedly breathed a sigh of relief. If they could have visualized the rest of the trip, the sigh of relief would have been replaced by a state of tizzy, until a telegram came saying "Arriving home on Flight X" (on a nice safe airplane).

Jan 1, 1946

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By G. P. Walters, W. C. Fuller

THE production of thin films of beryllium became essential early in the irradiation program at Harwell in order to study the fundamentals of irradiation damage in this metal. In common with other metals, electron-microacope specimens of beryllium can be produced by different techniques. The techniques used to produce thin-film specimens varied according to the starting material. Most of the starting material was -0.060 in. thick. Large-area specimens (1 in. long by 0.5 in. wide) were chemically thinned to -0.005 in. thick in a solution containing 85 pct orthophosphoric acid, 10 pct chromium trioxide, and 5 pct sulfuric acid at 70°C prior to electropolishing. Small-area specimens, Fig. 1, had to be mechanically thinned prior to electropolishing because chemical thinning considerably reduces the area as well as the thickness. Mechanical thinning tends to produce a worked layer about 0.002 in. deep and hence this method cannot be used to thin bulk specimens below about 0.005 in. thick. Mechanical thinning is carried out by mounting the specimen on perspex then carefully polishing on wet grinding papers. Polishing is continued until about half the initial thickness is removed; the reverse side is then polished in a similar manner. After the bulk specimens have been mechanically or chemically thinned to -0.005 in. they are elec-tropolished in the solution shown in able I at 50" to 80°C. This solution should be prepared by adding the chromium trioxide to the orthophosphoric acid and then the glycerol last. The glycerol should be added slowly because a vigorous effervescence can occur. Electropolishing is carried out by holding the specimen in stainless-steel tweezers and gently agitating in the solution. Masking or "window" techniques are not required for beryllium, good microscope specimens being obtained from the edges of elec-tropolished foils. A stainless-steel beaker should be used, acting as the cathode and solution container. A closed circuit voltage of 30 v is used for polishing. Too low a voltage produces a matt surface and pitting occurs when it is too high. The solution temperature is important. If it is too low, the solution is viscous and bad polishing results and, if too high, etching of the specimen occurs. After electropolishing, the foils are thoroughly

Jan 1, 1963

By H. W. Peirce

Identified and utilized Arizona salt deposits are of two ages: 1) Permian in the Colorado Plateau, and 2) Tertiary in the Basin and Range country. Uses include: a) storage of energy fluids in man-made solution cavities in both Permian (Supai Formation) and Tertiary (Luke salt body) salt and b) production of marketable products by solution and evaporation of tertiary salt. The two liquid petroleum storage Projects have a combined storage capacity in excess of 380 million L (100 million gal). Current production of salt products approximates 32 kt/a (32,000 stpy). Increasing demand for both storage and salt products is anticipated.

Jan 1, 1983

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By H. L. Sauder, J. L. Newman, C. Waddell

An instrument capable of measuring subsurface flow rates is described. The instrument is self-contained and may be run on piano wire line. It detects flow by means of an impeller suspended between two torsion wires. The force of the well fluid striking the impeller causes the impeller to rotate, exerting a torsional force to the wires. This force is determined by recording the angle of rotation of the impeller on film using a battery-driven, clock-controlled camera. The impeller is sensitive to flow in either direction and the same instrument can be used to measure injection as well as production rates. Changes in direction of flow, such as might be caused by thief zones, are measurable and are indicated by a reversal of the direction of rotation of the impeller. Adjustment of the sensitivity of the instrument to measure a wide range of flow rates is accomplished by the use of different size torsion wires. An umbrella-type fluid trap, which contacts the casing or wellbore, diverts the flow through the flow tube. The fluid trap remains closed while rurrning in the hole and can be opened at any point in the well. The instrument with the trap closed is 1 3/4 in. OD and may be run through 2 in. tubing. Successful flow profiles have been made on wells with flow rates ranging from 60 BID to 4,000 B/D at surface pressure up to 4,500 psi. The instrument is designed for high-pressure and high-temperature operations. INTRODUCTION The need for an instrument that will measure flow rates in a wellbore is as old as reservoir engineering itself. A number of such devices have been designed within the past few years. Some of these have been described in the literature1,2,3,4,5,6 One of these devices1. a hot-wire anemometer type, made many successful jobs in dry gas producing areas. Difficulty was encountered when this flowmeter was used in wells producing liquids and development work was initiated to overcome this difficulty. The present flowmeter is the result of this work and provides an instrument with a wider range of application in the industry. Consider- able development work has been done on the tool involving many changes in the mechanics of recording the flow readings, however, the basic principle of flow detection has remained the same since its inception. PRINCIPLE OF OPERATION The basic principle of operation of the flowmeter is the utilization of a portion of the kinetic energy of flowing well fluid to impart a rotational force to an impeller suspended between two torsion wires. This impeller, Fig. 1, is a screw-type propeller with the blades having a pitch angle of 40. As the well fluid passes through the instrument it strikes the impeller. The resulting force rotates the impeller and twist\ the torsion wires to a balance point at which the torque imparted to the wires balances the force required for the impeller to deflect the well fluid. The impeller is symmetrical and a change in direction of the flow results in a reversal of the direction in which the impeller is deflected. Thus the direction of the flow as well as its velocity is indicated. A dial is attached to the impeller by means of a hollow tube through which the upper torsion wire extends. The angular position of the impeller is recorded by photographing the dial at frequent intervals. In any given set of torsion wires the modulus of shear and polar moment of inertia remain constant and the deflection varies directly with the applied torque. The deflection imparted to the torsion wires also varies as the square of the fluid velocity. Further, the velocities represented by any two given deflections hear the following relationships: and Where V = velocity of flow stream and O ;= deflection. This is the basic relationship which is used to calculate the relative velocities represented by a given set of deflections where the velocity represented by any one of the deflection readings is a known quantity. For a given torque, the deflection of the torsion wire varies inversely as the fourth power of the wire diameter. Wire sizes ranging from ,005 in. in diameter to .022 in. in diameter can be used. The range of

Jan 1, 1957

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Jan 1, 1918

By V. Rajaram, I. P. Nielsen, H. D. Raymond

The Parachute Creek member of the Green River formation in the Piceance Basin, Colorado, contains vast reserves of oil shale, nahcolite, dawsonite, and other accessory minerals. The dry alkali process of sulfur dioxide removal using nahcolite (naturally occurring sodium bicarbonate) has great potential A room and pillar mining scheme has been designed to extract a nahcolite zone occurring at a depth of 472 m, from the lease application area of the Yankee Gulch joint venture. Geotechnical parameters affecting mine design will be discussed. A preliminary development plan for mining at the rate of 1000 t/d will be described in detail.

Jan 1, 1980

By S. Pearson, L. Rotherham

Measurements have been made of the variation of internal friction with temperature for OFHC copper, and for a series of binary solid solutions of high purity copper with zinc, gallium, germanium, arsenic, and silicon, to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity. The apparatus used was of the torsional pendulum type developed by KeI1 modified so that the specimen and vibrating system could be maintained in a high vacuum. The activation energy for grain boundary relaxation in copper is 33,000 cal per mol. This is considerably less than the activation energy for self-diffusion, in disagreement with Ke's theory2 that the two activation energies should be the same. All the alloying elements increase the activation energy for grain boundary relaxation to approximately 44,000 cal per mol, increasing the grain boundary viscosity at a given temperature. The results are discussed in terms of theories of grain boundary slip put forward by MottQ and by Ke.+ Experiments have also been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. EXPERIMENTS described in this paper were designed to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity, using the internal friction method developed by Kel for measuring grain boundary viscosity. It was considered desirable to make the system under investigation as simple as possible by making experiments on a comprehensive series of binary alloys of copper with the elements immediately following it in the periodic table, i.e., zinc, gallium, germanium, and arsenic. These elements are within the range of favorable size factor for solution in copper, and the systems have been extensively investigated by Hume-Rothery and his co-workers." Later, in order to study the effect of the relative size of the solvent and solute atoms, experiments were made on a series of Cu-Si alloys, since the apparent atomic diameter of silicon when in solution in copper—the diameter necessary to assign to the solute atoms to account for the lattice constant of the solid solutiona—is almost the same as that of the solvent atoms. Preliminary experiments were made to measure the variation of internal friction with temperature for pure copper. Ke made some experiments on copper," but found that the curves obtained were not reproducible in consecutive experiments. The copper was maintained in an argon atmosphere during the experiments but, although he took precautions to exclude oxygen, Ke came to the conclusion that the precautions were not entirely satisfactory, and that the lack of reproducibility must be due to absorption of oxygen by the copper. Experiments have therefore been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. Previous Work Ke made extensive experiments on high purity aluminum and was able to show that the grain boundaries behave viscously at high temperatures. He found that the relative rate of movement of the grains could be expressed as Where v is the velocity of slip, A is the constant, u is the shear stress, H is the activation energy, R is the gas constant, and T is the absolute temperature. By assuming that the boundary layer was one atom thick, he obtained a value for the viscosity which, when extrapolated to the melting point, gave good agreement with the viscosity of the liquid metal at the melting point. Ke also made experiments on other high purity and commercial purity metals:, and on some alloys." " He came to the conclusion2 that the activation energy for grain boundary slip was the same as for self or volume diffusion and for steady state creep in single crystals. Rotherham, Smith, and Greenough" have shown recently that the activation energy for grain boundary slip is not the same as for self-diffusion in tin,

Jan 1, 1957

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964