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By Francis Flynn

MANY excellent papers, descriptive of the milling and smelting of every kind of commercial ores, the refining of virgin metals, the casting into various shapes demanded by the trade, the rolling into shapes best suited to the factory machinery and the making of composition alloys to suit every requirement have been issued by the many technical societies dealing with non-ferrous metals. It is a wonderful collection of papers, of which the mining and metallurgical engineers may well be proud, but strange as it may seem, metallurgists in general appear to take the stand that when they have delivered suitable alloys to the foundry and rolled products to the factory their duty to write papers has ceased, at least in so far as the A. I. M. E. is concerned. Still we read in the daily papers that the mining companies are absorbing metal-manufacturing industries. The purpose of this paper is to describe the reclaiming of non-ferrous scrap metals at manufacturing plants, taking as an example the automobile industry.

Jan 1, 1929

By Norman Yarborough

Much has been written about the energy fuels including their standing with respect to reserves, their delivered Btu costs, their potential in the electrical generating market and their capabilities to meet a burgeoning demand. Yet, when all factors are placed in their proper perspective, the spiraling electrical energy market alone should guarantee each fuel a better than average market for the foreseeable future. In fact, a study made by the U.S. Federal Power Commission on the spare capacity utilities have on hand indicated that 39 of the 181 major utility systems had less than 10% reserves on hand at the end of 1969. Fuel supplies are critically low in some areas, especially in the Southeast, South Central and Midwest areas of the U.S. In other systems equipment shortages resulting from faulty equipment or delays in getting new equipment deliveries causes power failures during peak loads. In addition, lack of labor curtails the erection of some new facilities and prevents many other facilities from operating at capacity.

Jan 1, 1970

By R. A. Morse, P. M. Bridges, L. E. Wilsey, Howard N. Hall, P. L. Terwilliger

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By L. E. Wilsey, R. A. Morse, P. L. Terwilliger, Howard N. Hall, P. M. Bridges

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler's saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

J. M. Wadsworth,' Okmulgee, Okla. (written discussion).—It seems to me that thc young man must first be absolutely sure that the work he has taken up is to his liking and then I would advise that he get into the practical end of it and learn as much about it as he can as fast as he can. For instance, in the refinery business the college man, graduated in chemical engineering, should ground himself by going through the various departments in a refinery and working in them until he is thoroughly familiar with the operating problems. In a short time he would be able to apply many things which appear in the abstract form in his college work and this would opcn up an opportunity for him to capitalize on them, promoting his own interest. I do not criticize the present-day college men as a class, but I have found that many of them come into your plant with the idea that mere possession of a diploma should insure rapid promotion; in a short time they are impatient and usually leave. We have found in employing men that the single attribute most difficult to find in them is a lot of energy and whole-hearted interest in the work at hand, and it seems to me that if a man combines these with a careful technical training he should be fairly well equipped to gamble on his future. They must learn that the biggest satisfaction to be gained in life is in their work. Procedure for Attaining Objective of Young Petroleum Engineer H. B. Fell,+ Ardmore, Okla. (written discussion).—Of course, the first thing to be ronsidered in any proposition is the ultimate objective that is desired to be attained. 1 presume that the desired objective of most of the young men graduating in petroleum engineering will be that of chief executive of one of the companies in the petroleum industry, or one of the allied industries, or to become an independent oil producer, or oil refiner, or possibly an oil distributor. The next phase then to be considered is the procedure which should most logically be followed to attain the objeckive of the indivitlual, since in these cases these young men will have been trained in a course in petroleum engineering and it would logically be presumed that the attainment of their objective should be through the operating end of the branch of the business with which they are connected. The operating end is, of course, the department of each branch of the business that develops the resources, or refines the products, or distributes the products, from which the profits are derived, and is a part of any business which is filled with enough interesting work to appease the desires of the most ambitious young men. In order to get the best possible training it would appear to me that the place for a young man to start after graduation would be at the bottom of that branch of the industry which he expects to follow. For example, if he is going in the producing end he can gct no better training than is secured by starting as a roustabout in the ficltl, where he romes in constant rontact with the character of work that is necessary

Jan 1, 1928

By H. M. Wilten

THIS article presets a view of a problem encountered in petroleum refining in the deterioration of equipment used in condensation of vapors and cooling of liquids. Discussion is limited to the problems of shell- and tube-type exchangers and condensers. In this service shell- and .tube-type equipment is gradually displacing other types and, for this reason, its economic importance ill oil-refining practice is also increasing. Considering oil - refinery practice during the last two decades one can readily see many important improvements in the apparatus used. Briefly, the present equipment is safer, more efficient, and Ignore economical. Improvement in apparatus used for the condensation of distillates has, in my opinion, been less than that in other essential distilling apparatus. So it is hoped that this discussion will stimulate research among the producers as well as among the consumers of this equipment with a view to ameliorating this condition.

Jan 1, 1937

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

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By Charles J. Speake, Dennis R. Haley, Thomas E. Finch

The tremendous interest in development of surface- mineable coal throughout the western US will bring with it a requirement for many manhours spent in mine planning and equipment selection. One problem in particular that engineers face during the planning stage is that of selecting a dragline with the proper reach capability. Reach, expressed in terms of operating radius and effective spoil radius, can be a major problem when mining deeper than originally planned, and aside from production requirements, the ability of a particular dragline to spoil across a strip is essential. Determination of dragline reach needed for a multiple-seam western coal operation can be simplified by use of an equation derived below that eliminates the need for tedious and repetitive calculations.

Jan 5, 1977

By J. S. Ll. Leach, M. B. Bever

THE system copper-nickel exhibits complete solid and liquid miscibility1 The thermodynamic properties of such a system would not be expected to deviate greatly from ideality. Although the evidence is conflicting, anomalies in the composition dependence of various physical properties of solid copper-nickel alloys suggest that mixing may not be ideal.' From measurements of the Hall coefficient it has been concluded that clustering occurs in these alloys. ' Considerations involving the phase diagram of the ternary system copper-nickel-chromium have led Mei-jering3 to predict a positive heat of formation for solid copper-nickel alloys. An electrochemical investigation of the activity of nickel in copper-nickel alloys showed unexpectedly large positive deviations from ideality.4 wagner5 has proposed that if the entropy can be considered ideal, these measurements would yield the following equation for the heat of mixing at 700°C H" = 3380 x,vl (l-xVi) cal per g atom [I1 The heat of formation at 722°C of solid copper-nickel alloys of the equiatomic composition has been measured in a reaction calorimeter as 540 cal per g atom. This note reports calorimetric measurements of the heat effects on dissolution of some copper-nickel ndon: in tin. These measurements were preliminary to a larger investigation, which was later discontinued. From them the heats of formation of the alloys can be calculated, if certain assumptions are

Jan 1, 1960

By E. L. Raymond

The effect of heat treatment on the microstructure and resultant notch-bar rupture life of ZNCONEL alloys X- 750 and 718 was studied. It was found that the primary effect of heat treatment in rendering these alloys notch-ductile is the elimination of any y' denuded zone adjacent to the pain boundaries. The mechanisms by which such a denuded zone can arise and be eliminated by heat treatment are discussed. InCONEL Ni-Cr alloy X-750 and INCONEL Ni-Cr alloy 718 are age-hardenable austenitic materials. Alloy X-750 is used for its corrosion and oxidation resistance and high creep-rupture strength up to 1500°F. Alloy 718 is used most effectively up to 1300°F. One of the most important areas in their development has been establishment of consistently good rupture properties, especially in the presence of a stress concentration, such as imposed by a notch. A desire to improve these properties has led to extensive studies of the effect of heat treatment on the micro structure of these alloys and their performance in stress-rupture tests. In earlier investigations"~ of INCONEL* alloy X-750, *INCONEL i s a Registered Trademark of The International Nickel Co., Inc. grain boundary carbide morphology was linked with stress-rupture properties. If, during heat treatment, the carbide MZSC was precipitated in the grain bound-ary in a cellular form, poor rupture properties re-

Jan 1, 1968

By Charles Maier

PART I DENSITY AND ENERGY CHANGES IN COLD-WORKED COPPER IT has long been supposed that when crystalline materials are com-minuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led' to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1. The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chem-ical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the cor-rected heat of solution was less for fine material than for coarse. Con-tinuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. Similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by

Jan 1, 1936

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By M. King Hubbert, David G. Willis

A theoretical examination of the fracturing of rocks by means of pressure applied in boreholes leads to the conclusion that, regardless of whether the fracturing fluid be of the penetrating or non-penetrating type, the fractures produced should be approximately perpendicular to the axis of least stress. The general state of stress underground is that in which the three principal stresses are unequal. For tectonically relaxed areas characterized by normal faulting, the least stress should be horizontal; the fractures produced should be vertical with the injection pressure less than that of the overburden. In areas of active tectonic compression, the least stress should be vertical and equal to the pressure of the overburden; the fractures should be horizontal with injection pressures equal to or greater than the pressure of the overburden. Horizontal fractures cannot be produced by hydraulic pressures less than the total pressure of the overburden. These conclusions are compatible with field experience in fracturing and with the results of laboratory experimentation. INTRODUCTION The hydraulic-fracturing technique of well stimulation is one of the major developments in petroleum engineering of the last decade. The technique was introduced to the petroleum industry in a paper by J. B. Clark,' of the Stanolind Oil and Gas Co. in 1948, and since then its use has progressively expanded so that by the end of 1955 more than 100,000 individual treatments had been performed. The technique itself is mechanically related to three other phenomena concerning which ah extensive literature had previously developed. These are: (1) pressure parting in water injection wells in secondary-recovery operations, (2) lost circulation during drilling, and (3) the breakdown of formations during squeeze-cementing operations, all of which appear to involve the formation of open fractures by pressure applied in a wellbore. The most popular interpretation of this mechanism has been that the pressure had parted the formation along a bedding plane and lifted the overburden, notwithstanding the fact that in the great majority of cases where pressures were known they were significantly less than those due to the total weight of the overburden as determined from its density. Prior to 1948, this prevalent opinion had already been queried by Dickey and Andresen,2 in a study of pressure parting; and by Walker,"' who, in studies of squeeze cementing, pointed out that the pressures required were mostly less than those of the overburden, and inferred that the fractures should be vertical. J. B. Clark,' in his paper introducing hydraulic fracturing, and later Howard and Fast," and Scott, Bearden, and Howard," also of Stanolind, postulated that the entire weight of the overburden need not be lifted in producing horizontal fractures, but that it was only necessary to- lift an "effective overburden," requiring a correspondingly lower pressure. Hubbert,7 in discussing the paper by Scott and associates, pointed out that the normal state of stress underground is one of unequal principal stresses; and in tectonically relaxed areas, characterized by normal faults, the least stress should be horizontal. Therefore, in most cases, fracturing should be possible with pressure less than that of the overburden and, moreover, such fractures should be vertical. Harrison, Kieschnick, and McGuire,8 also on the expectation that the least principal stress should be horizontal, argued strongly in favor of vertical fracturing. Scott, Bearden, and Howard6 observed that, when

Jan 1, 1958

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By Job Goostray

IN THIS paper, as in so many other discussions of historical nature, there is little chance for original material and much has had to be rewritten from older papers, documents, accounts, reports, and the like, some of which are of doubtful authorship or contain conflicting statistics. Fully aware of these little historical pitfalls, the authors have tried to quote the origin where possible, and also to seek further confirmation when the statement warranted it, but cannot assume responsibility for certain facts and dates. The Encyclopedia Britannica was frequently consulted. The authors wish to acknowledge assistance from MacKintosh-Hemphill Co.-formerly the Fort Pitt Works-and also from officials of the Watertown Arsenal who loaned valuable books and gave much necessary information. They are particularly indebted to Colonel Dixon of that institution. The data on modern guns were furnished by Mr. F. Brauer of the Watertown Arsenal; Mr. H. S. Chaffee assisted by obtaining records and data of work carried on by the Builders' Iron Foundry of Providence, R. I.

Jan 3, 1925

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By W. B. Nelligam, J. Tittman

Refinements in radiation logging techniques during recent years have involved increasing usage of scintillation ditectors. These detectors produce voltage pulses whose heights are related to the energies of the gamma rays which initiate them. Analysis of the gamma-ray spectrum, as indicated by the pulse heights, yields information about the chemical elements composing the formations surveyed. Refined scintillation counter techniques can furnish chemical information concerning earth formations in situ, from a study of the gamma-ray spectra emitted by the formation either naturally or as a result of neutron bombardment."' Accompanying the rising interest in gamma-ray scintillation spectroscopy, there has been increased activity in the development of accelerator-type neutron sources (in contrast to encapsulated chemical-mixture sources). Such neutron generators are attractive for several reasons: (1) they greatly reduce radiation hazards to personnel; (2) there is a great reduction in contamination danger if they are lost in the hole; (3) they can produce larger neutron intensities than can conveniently available encapsulated sources; and (4) they are capable of being pulsed, thus permitting new techniques in logging. In the past, both accelerator and encapsulated neutron sources have been used by others in conjunction with scintillation-detector pulse-height analysis. The results have not been too encouraging, due to the interference among different gamma-ray spectral lines and to the fact that the gamma-ray peaks were not too clearly distinguishable above the large and ill-defined background "noise".'.' This paper is a status report on laboratory studies of a technique using a borehole accelerator as a neutron source, which gives an improved scintillation spectrum, thus permitting more accurate chemical analyses of the formations penetrated. The Schlumberger-accelerator neutron source' is presented; the origins of inelastic and of thermal-neutron, capture gamma rays are dis- cussed, and results are given for some laboratory measurements performed in borehole geometry. THE NEUTRON GENERATOR-TUBE ACCELERATOR In the attempt to develop an accelerator neutron source which would have the desirable properties outlined in the "Introduction" and which would operate satisfactorily under borehole logging conditions, a small-diameter, cylindrical, neutron generator tube has been developed. This tube utilizes the principle of accelerating deuterons (heavy hydrogen nuclei) by a high voltage so that they bombard a tritium (heavy, heavy hydrogen) target. The resulting reactions produce large numbers of neutrons of 14 Mev energy. Furthermore, the tube is permanently sealed and, thus, the use of pumping techniques in the sonde is avoided. The tube consists of a pressure control, an ion source in which the deuterons are stripped of their electrons, an accelerating gap down which the deuterons are sped by the high voltage, a secondary electron suppressor and a tritium-loaded target. Obviously, the tube requires auxiliary circuitry in a sonde for the control of the ion source, tube pressure, high voltage and other operating variables. Neutron yields, both continuous and pulsed, have been produced under simulated field conditions in the range between 1 and 10 times those conventionally used in neutron logging applications. For the experiments discussed in this paper, neutron-pulse repetition rates in the range between 500 and 5,000 pulses/sec are adequate. Furthermore, by making suitable adjustments in operating conditions, one can vary the pulse width from a minimum of several microseconds up to dc. As will be seen later, the present application to well logging does not require that one have available pulses of neutrons which are appreciably shorter than the time it takes for fast neutrons to slow down to thermal energy in water. As a consequence, much of our interest has been directed towards the operating characteristics of the tube with pulses longer than about 10 microseconds in duration. Our experience to date shows that tubes can be operated in this manner with reasonably constant, average neutron outputs.