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By D. I. Bardos, A. M. Bardos, Paul A. Beck

The approximate effective silicon radii in ternary Laves phase alloys with transition elements and silicon were found to range between 1.16 and 1.21A, i.e., considerably smaller than the atomic radius calculated for elemental silicon. The atomic radii were found to increase with the size of the transition element atoms in the structure. It has been noted by Aronsson1 that silicon in solid solution in iron, cobalt, and nickel has an effective CN 12 atomic radius of approximately 1.20Å, a value very much smaller than the CN 12 radius of 1.34Å derived from the interatomic distances in elemental silicon.7 The unusually short metal-silicon interatomic distances in transition element monosilicides and disilicides have been also pointed out by various investigators.1 A similar tendency was observed by Nevitt in Cr3O type silicides.2 Recent work on Laves phases in ternary systems of silicon with transition elements4"8 suggested that extensive Laves phase fields may occur in such systems.8 It has been pointed out by Laves7 that the MgCu2 and MgZn2 type structures lend themselves particularly well for the determination of the effective radii of the component atoms. In these AB2 phases the B atoms are arranged in close packed straight lines, and their distances are related in a simple manner to the lattice parameters.8 The present work was undertaken in order to find out whether or not the B transition element in such AB2 Laves phases can be replaced to an appreciable extent by silicon. In cases where extensive substitution proves to be possible, the "average atomic radius for the B site" at various silicon contents was to be determined, and the effective atomic radius of silicon calculated by extrapolation to complete replacement of the B component by silicon. The following ternary systems were studied: Ti-Mn-Si, Ti-Fe-Si, V-Co-Si, V-Ni-Si, Nb-Fe-Si, Nb-Co-Si, Ta-Fe-Si, Ta-Co-Si, and Mo-Fe-Si. In all of these alloy systems, the Laves phase solid solutions were found to extend over a considerable range of silicon content. As previously reported,4"8 in the V-Co-Si, V-Ni-Si, and Mo-Fe-Si ternary systems Laves phases do occur, even though there are no corresponding binary Laves phases. In stabilizing the Laves phase, silicon acts as if it were decreasing the effective electron concentration of the alloy.8 A more detailed study of the boundaries of the Laves phases in the V-Co-Si and V-Ni-Si systems has been made and will be published elsewhere. In both cases, the elongated Laves phase fields extend parallel to the B-Si side of the composition triangle, clearly showing that silicon is substituting for cobalt, respectively, nickel over a wide range of compositions. The binary Laves phases NbCo2 and TaCo2 have the cubic MgCu2-type structure. It was found that, in both ternary systems with silicon, again the MgZn2-type hexagonal Laves phase is stabilized and that this phase extends to high-silicon contents. In each ternary system at least three Laves phase alloys of the composition A(B1_xSix)2 were used, x here denoting the fractional substitution of the B-transition element atoms by silicon. The alloys, listed in Table I, were prepared by arc melting in argon. Each specimen was water quenched after a homogenizing anneal of 3 days at 110(FC, except for the Mo-Fe-Si alloys, which were annealed at 1200°C. Metallographic examination showed that most of the homogenized alloys consisted of a single phase, although some had minor amounts of a second phase, as shown in Table I. X-ray diffraction patterns were prepared using an asymmetrical focusing camera of large resolution and Fe Ka radiation. The patterns were indexed, and the lattice parameters of the hexagonal Laves phases were determined from the available diffraction lines of highest indices: (213), (205), and (313). The lat-

Jan 1, 1963

By G. A. Vissac, R. G. Minet, N. E. Sylvander

R. G. Minet—The authors' description of the remarkable progress made in the last few years in applying the fluidized solids technique to the problem of lignite drying and carbonization clearly demonstrates that engineering techniques available today may make many processes practical and profitable which a few years ago were considered otherwise. As pointed out in the article, the future of the carbonization step hinges on the value and utilization of low temperature tar. On paper, at any rate, this tar looks like a valuable raw material for the chemical industry to use. Some 50 to 60 pct may be converted to pitch for electrodes, roofing, road tars, and other valuable products; the 25 to 30 pct tar acids could conceivably form a basis for a new low cost resin or plastic of the phenolformalde-hyde type. Yet these materials are so new and dissimilar from available sources that much work must be undertaken by the chemical industry before they will be accepted. Now that the work of Dr. Perry and his colleagues has made a large supply of low temperature tar a real possibility, I would expect the chemical industry to accelerate its work in this field. On the basis of certain data available in the literature it appears possible to produce a more aromatic tar, although in smaller yield, by operating at temperatures in the range of 1300" to 1500°F. Operating a fluidized bed process for lignite at these conditions should be technically possible, at least, and could produce a tar having more familiar characteristics. I wonder if Dr. Parry would care to comment on such a possibility. Incidentally, in our own work on carbonizing coking coals in fluidized beds, using Ohio, Pennsylvania, and West Virginia high volatile bituminous coals, we have obtained yields which agree with the correlation given for tar yields vs moisture and ash-free volatile Btu. Our data are slightly under the line, but certainly in the range of the correlation. We have also obtained evidence in support of the authors' statement as to the effect of air on the process. In our pilot plant all the heat required for carbonizing is released by internal combustion of char in the fluidized bed in normal operation. We are also equipped to obtain all carbonization heat by external electric heaters on the shell of the carbonizer while introducing only an inert gas to the process. We note no difference in tar yield or characteristics between the two operations. In the case of the gas, however, it appears that some hydrogen is consumed by the air combustion. We would be interested in hearing in a little more detail about the hot dust and char handling problems at Sandow. Have the authors found char subject to spontaneous combustion? Have they ever tried a coking coal in their pilot plant? V. F. Parry (author's reply)—Production of a more aromatic tar by operation of the carbonizer at 1300" to 1500°F does not appear to be economical. 1) The capacity of a reactor operating at 1500°F would be 30 to 50 pct less than the capacity at 932 °F and the cost of processing would increase materially. 2) The cracking of tar vapors in a reactor requires appreciable time to complete the reactions and it is doubtful that considering the very short time of residence of tar vapors within the reactor (4 to 10 sec after evolution) the basic character of the tar would be changed significantly. This is indicated from the data reported in Table XIV. 3) General studies have shown that it is advisable to operate at the minimum temperature to produce the maximum tar and minimum gas. 4) Operating problems and the maintenance of vessels and reactors, and the hazards of handling hot char, increase with the temperature of carbonization. It is technically possible to operate at temperatures as high as 1500°F, but in my opinion it is not economical or desirable. We believe that the primary tar must be won in the simplest way and then processed alone to change its character for production of desired products. It is interesting to have confirmation of our observations on the reaction of air with the products of carbonization. The major reaction is with the char, fol-

Jan 1, 1957

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °', showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000'C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid' identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.' In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By F. F. Schmidt, H. R. Ogden, E. S. Bartlett

Continuing tantalum alloy development studies have been concerned with a more detailed investigation of promising binary, ternary, and more complex tantalum alloys containing Groups IV-A, V-A, VI -A. VII-A, and VII-A metal additions. A primary objective of these studies was to improve the elevated temperature strength of tantalum with minimum degradation of fabricability and low-temperature ductility by alloying. Several alloys were found to exhibit hot tensile strengths in the excess of 25, 15, and 10 ksi at 2700°, 3000°, and 3500°F, respectively, combined with excellent cryogenic toughness and ductility. Particularly outstanding in this respect are alloys in the system Ta-Mo-W. Ternary parameter curves describing hot-strength, low-temperature ductility, recrystallization temperature, weld ductility, and fabricability are presented for the Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W systems. At present, only four metals qualify for large scale structural applications at temperatures above about 1800°F. These are tungsten, tantalum, molybdenum, and columbium. Research and development work on these refractory metals has progressed to the point where efforts are now primarily directed toward the improvement of high- and low-temperature mechanical properties through alloying. High melting point combined with excellent low-temperature ductility, fabricability, toughness, weldability, and high solubility and tolerance for both substitutional and interstitial solutes are important attributes of tantalum. Conversely, its high density and relative scarcity compared with other refractory metals are the major deterrents to the use of tantalum. Early studies in the Battelle alloy development program established base line data on the mechanical and metallurgical properties of high-purity tantalum.' These studies were extended to include a preliminary investigation of the effects of various alloying elements on the established base properties.2,3 Recent studies involved a more detailed investigation of promising binary alloys containing Cb, Hf, Mo, Os, Re, Ru, and W, and ternary Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W alloys. Results of major importance obtained are given in this article. EXPERIMENTAL PROCEDURES Electron-beam-melted tantalum (Wah Chang) and high-purity alloying elements were consolidated as 150-g ingots by multiple nonconsumable arc melting under a partial atmosphere of helium. Homogeneity of the button ingots was checked radiographically. Alloy buttons measured about 1-1/2 to 1-3/4 in. in diam by about 0.35 and 0.50 in. thick. Nominal alloy compositions were checked on each alloy button by weighing after arc melting. In most instances, weight losses were within 3 pct of the total weight charged. Subsequent chemical analyses on a number of selected alloys showed interstitial contents to range as shown below: Range of Interstitial Content, ppm 0 C N H 25-75 50-100 10-50 1-5 Metallic alloying additions were found to agree well with nominal compositions based on weight change data. Fabrication directly from the cast button to sheet was conducted at low (75° to 900°F), intermediate (1800° to 2000°F), or high (3000°F) temperatures, depending upon alloy content and hardness. Evacuated stainless steel or molybdenum packs were used for fabrication at intermediate and high temperatures, respectively. The temperature required to complete recrystal-lization in one hour was determined by hardness measurements and metallographic observations (longitudinal test sections) after vacuum annealing at 180°F intervals in the range 2010° to 2910°F. All mechanical property evaluations were conducted on recrystallized sheet, nominally 0.04 in. thick. Weldability of the various alloys was screened using manual TIG welding techniques. Bend ductility (bend axis perpendicular to weld axis) was the criterion used for evaluation. Tensile specimens employed 0.200 by 1 in. gage lengths, and bend test specimens measured about 1 by 1/4 in. Low-temperature tensile tests were conducted using a crosshead speed of 0.02 in. per min up to the point of yielding, and 0.05 in. per min to fracture. High-temperature tensile tests were conducted in vacuum using a crosshead speed of 0.01 in. per min

Jan 1, 1963

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase

By E. D. Gardner

FIFTY years ago the Utah Copper enterprise at Bingham was just getting under way. An epic in metal mining was in the making. Throughout the West the bonanza deposits were approaching exhaustion and most ore still went direct to smelter. But concentrators were shortly to be constructed for treating milling grade ores, and most important, the pilot plant for the Utah Copper enterprise was being built that year at the mouth of Bingham Canyon. The same decade was to see development at the Inspiration mine in Arizona of the most important new mining method for 50 years to come—undercut block caving. Although the average grade of ore being mined has been declining for 50 years, and wage rates and prices of supplies have been greatly increased, the mining industry has continued to grow and to prosper. Technology has advanced to a point where minerals can be mined under the most severe conditions. The hardest rock can be drilled and broken and the heaviest ground handled. Large or small, an ore-body can be mined successfully, at any desired rate of production. It is possible to pump great volumes of water and to ventilate the most extensive workings; air conditioning has made practicable the mining of ore where the rock temperatures are beyond those that can be borne by man. Mining today in the U. S. is a huge earth-moving operation. In 1953 nearly 2 billion tons of material were mined for direct use or for processing. Stripping at open-cut mines totaled about 1.7 billion cu yd. Table I gives relative tonnages of the branches of the mineral industry in 1953. In addition to the solid materials moved, 350 million tons of petroleum and 340,000 tons of gas were produced in 1953. Fifteen million tons of salt and 5 million tons of liquid sulphur were pumped from wells. An appreciable amount of copper was recovered by leaching old mine workings and dumps. Total value of minerals produced in 1953 was $14.4 billion: oil and gas $7.6 billion, coal $2.6 billion, nonmetallics $2.4 billion, and metals $1.8 billion. Formidable problems face some branches of the industry today, especially pertaining to increased output tons per manshift. The time has come when these problems should be reappraised. With current wage rates, the industry no longer can afford to pay men to do manual labor. It should be recognized, also, that the miner is a skilled worker; efforts to promote the dignity of his calling and his pride of accomplishment have yielded beneficial results. Mineral deposits occur under widely varying conditions. In most instances the degree of support needed by the roof and walls is the deciding factor in selection of an underground mining method. The degree of support needed, in turn, is governed by natural physical characteristics of the ore and its enclosing rocks. Mine operators, of course, learn to judge ground by observation, and an experienced mine boss generally can anticipate what will happen following any given mining operation. A more scientific approach, however, would be advantageous in most cases. More should be known about the strength of the ore and the enclosing rocks, more about stresses set up in the ground when ore is removed, and more about the mechanics of moving ground. Better understanding would work both ways: first, favorable rock conditions could be fully utilized for more efficient mining, and second, hazards of rock falls could be minimized, loss of ore in mining reduced, and expenses caused by ground pressures and subsidence lowered. In general, mining comprises breaking the ore or rock in place, supporting the mine workings, and transporting the ore to the surface. This latter is a materials handling problem. Ventilation, of course, must be provided, and the mines must be kept free of water. Development work at some places is the most important cost item in extracting ore. Drilling and blasting remain the usual practice for breaking ore or rock from place except, of course, at block-caving mines. The drilling and blasting practice at a mine must fit the mining method. In laying out mining procedures attention is being given to

Jan 1, 1956

By H. E. Cline, E. F. Koch, J. L. Walter

It has been postulated and, in a few instances shown, that some kind of dislocation structure will be present at semicoherent interfaces to accommodate small lattice mismatches. In the present study of the NiAl-Cr eutectic, regular arrays of interface dislocations are observed at the boundary between the chromium-rich rods and the NiAl-rich matrix. The networks were examined by transmission electron microscopy and selected area diffraction. The rods and the matrix have a crystallographic relationship in which all directions and planes of the two phases are parallel. The dislocation networks are cmposed of a<100> dislocations lying on the intersections of the cylinders with (100) planes. Dislocations forming hexagonal rather than square arrays are also observed at certain areas of the network. The morphology of the network is consistent with the interpretation of mismatch being accommodated by interface dislocations in the cylindrical geometry. The measured spacing between dislocations was used to calculate an apparent lattice mismatch between the phases (˜0.35 PCt)interface network energy (-140 ergs per sq cm), and network strengthening (-10,000 psi). It has been proposed by Frank and Van der Merwe1 that dislocations should be present at the boundary between two semicoherent crystallographically related phases. The role of the interface dislocations would be to reduce the internal stresses, caused by the mismatch in atomic spacing across the interface. Such dislocations have been observed at the interface between expitaxially grown films and Substrates.2-4 Interfacial dislocations have also been observed at precipitate-matrix interfaces.&apos;-&apos; Directionally solidified eutectics have been shown to have semicoherent phases1&apos; and would, therefore, be expected to have interfacial dislocations as found by Weatherly at a lamellar fault in A1-A12Cu.11 The NiAl-Cr eutectic appeared to be a promising system to examine because both phases are cubic, the lattice mismatch is small, and the phases are crys-tallographically related. Furthermore, the eutectic is easily thinned for transmission microscopy. Indeed, interfacial dislocations were observed and this report describes the nature of the dislocation networks in the boundary between the NiAl-rich ma-trix-phase and the fine chromium-rich rods.21 I) EXPERIMENTAL PROCEDURE Ingots, 3/4 in. in diam and 6 in. long were made by melting in vacuum and casting under argon using 99.9 pct pure material. The composition, in at. pct, was 33 pct Ni, 33 pct Al, and 34 pct Cr. The ingots were then placed in A1203 crucibles on a water-cooled base, melted by means of induction, and withdrawn from the hot zone at the rate of 1 in per hr under argon.* * T his material was first directionally solidified in this laboratory by E. R. Stover Slices were taken perpendicular to the growth direction of the directionally solidified ingot for metallography and for transmission electron microscopy. The electron transmission samples were thinned mechanically, then thinned electrolytically in A-2 electrolyte* *A-2 electrolyte: 62 ml perchloric acid, 700 ml ethanol, 100 ml butylcellosolve, 137 ml distilled H20. until a hole appeared in the foil. 11) EXPERIMENTAL RESULTS A) Optical Microscopy. The microstructure, viewed on a plane perpendicular to the growth direction, is shown in Fig. 1. The structure consists of cells or colonies of parallel chromium-rich rods in the NiAl matrix. The cells occur when there are impurities present12 or, in a ternary eutectic, if the composition is slightly off the eutectic composition. The axis of the chromium-rich rods is parallel to the growth direction except near the cell boundaries. Here the rods may assume angles to the growth direction; however, examination shows that the crystallographic relationship between the rod and the matrix remains the same. Fig. 1 includes cell boundaries where the rods formed at a large angle to the growth direction. The variation of rod position across the cells made it possible to Fig. 1-Structure on plane perpendicular to growth direction. Rods near cell walls are at large angle to growth direction. Magnification 315 times.

Jan 1, 1970

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.&apos; It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.&apos; The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:&apos; A similar treatment has also been reported to apply to zinc sulphide ores.&apos; It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.&apos; The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, &apos; AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.&apos; The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay&apos;s rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into &apos;&apos;high", &apos;&apos;medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4&apos;6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~&apos; for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By F. Garofalo

It has been shown by various investigators that during constant stress creep the dependence of minimum creep rate, 6,, on stress, o, is given by em = A onat low stress levels, md by 6, = A&apos; exp [ß s] at high stress levels. In these relations A, n, A&apos;, and ß are constant at constant temperature. A single relation has been found which satisfies conditions for both high and low stresses and agrees well with experimental results. This relation is 2, = AN (sinh a s)n, where A" is a constant at constunt temperature and a = p/n. This relation also satisfies the linear relation, 6, = k s, found at temperatures near the melting point at low stresses. EXPERIMENTAL creep results have led to a number of empirical relationships between minimum creep rate, 6,, and the applied stress, s. Under conditions of constant stress it is generally found that at low-stress levels,&apos;-&apos; the dependence of minimum creep rate is given by 6, = Asn. At high-stress levels&apos;74 the experimental results fit the relation, 6, = A&apos; exp [po l. In these relations A, n, A&apos; and ß are constant at constant temperature. A model based on climb-of-edge dislocations from a pile-up array leads to a relation similar to that found experimentally at low stresses.&apos; On the other hand. theories based on chemical-reaction rate,5 nonconservatively moving dislocation jogs, and jog migration and climb-of-edge dislocations4 lead to a relation similar to that found experimentally at high stresses. No difference in mechanism between low and high stress levels has been clearly defined; it is questionable whether such a difference really exists. In any event, the major argument usually given in substantiation of a change in mechanism from low to high stresses is that no single relation exists for defining the stress dependence of the creep rate over wide ranges in stress. However, such a relation has been found and is of the form, dm = A" (sinh a s)n, where A" is a constant at con- stant temperature and a = ß/n. This relation agrees well with experimental results over wide ranges in stress and temperature for copper, aluminum, an A1-3.1 pct Mg alloy, and an austenitic stainless steel. STRESS DEPENDENCE OF MINIMUM CREEP RATE At low stress levels the minimum creep rate, gm, depends on the stress, 0, under conditions of constant stress creep through the relation em=Aon [1] The quantities A and n have been defined previously. In the range in which this relation applies, a linear dependence is found in a log em,-log o plot. Above the stress range of application of relation [I], the minimum creep rate increases much mar; rapidly than predicted by relation [I]. This behavior is shown in Fig. 1 for a series of creep tests on copper4 at various temperatures ranging from 673 o to 973°K. Relation [I] is satisfied at the lower stresses, although the results at 973°K are quite limited. In all cases the transition beyond the applicable range of relation [I] is a gradual one indicating no abrupt change in mechanism. For all test temperatures, values of n have been determined from the results in Fig. 1. These are reported in Table I under Alog tm/hlog o. At high stress levels the stress dependence of minimum creep rate under conditions of constant stress is given by im = A&apos; exp [ß a] 2] All factors have been defined previously. In a log em-0 plot, relation [2] predicts a linear function. Experimentally, a pronounced deviation from the prediction of relation [2] is found at lower stresses. As the stress is lowered, the minimum creep rate decreases more rapidly than predicted by relation [2]. This shown for copper in Fig. 2. Again it is found that the transition from high to low stresses is gradual and no really sharp change is found. Values of p determined from the high stress results are given in Table I. The dependence of minimum creep rate on stress at constant temperature for all ranges in stress

Jan 1, 1963

By F. J. Haller

IN 1943, we found, in the new Mather operation, a very unusual and disappointing condition in the footwall rock where all of our main haulageways were to be located. With the exception of a few hundred feet out of the thousands then planned and since driven, all of the openings require support. In general, the ground is not particularly heavy, at least by our standards, but it must be supported and the back carefully covered. Also, our operations require rather wide plat openings (16 to 18 ft) and rather flat curves at the turn-outs, all of which adds to the problem. When this completely unforeseen condition was discovered, ordinary timbering was the only answer, because of the impossibility of obtaining adequate steel supplies in time due to war shortages. Then by the time steel supplies were obtained and a practice developed, we found ourselves with between four and five miles of main haulage drifts and plat openings of a permanent nature, all of which were supported by hardwood timber, some of which had already rotted to an unsafe degree. Also, our drifting program was adding some two miles per year to the above figure. F. J. HALLER, Member AIME, is Superintendent, Mather Mine, Cleveland-Cliffs Iron Co., Ishpeming, Mich. AIME Columbus Meeting, September 1949. TP 2840 A. Discussion (2 copies) may be sent to Transactions AIME before May 31, 1950. Manuscript received Aug. 22, 1949. Revision received Jan. 17, 1950. To give all of the details of our experiments, studies, and experiences would fill a large book, but we were satisfied that our organization had done an excellent job, starting from scratch. You can appreciate our surprise when we discovered that we had added very little to an existing record. Attention was called to a footnote in a copy of "Carnegie Pocket Companion" year 1923. The note read: "Full information as to uses of H-Beams is given in pamphlet entitled &apos;Steel Mine Timbers.&apos; " A search of our Engineering Library brought to light a pamphlet printed in 1911 showing extensive use of steel for this purpose. Except for welding in place of riveting, we have added very little to the designs in that book. We have, however, developed an experience which proves, at least to our own satisfaction, that steel mine supports pay off under the proper conditions. We are now convinced, in spite of the relatively high initial cost of materials, that steel sets, because of comparatively low installation cost, are actually cheaper than either treated or untreated wood sets, if they are properly designed and adapted. Several Sections in Use: Convenience guided our first experiments in steel sets, since for a number of years, we had used the 4-in. WF, 10 lb per ft section in 10-ft lengths as safety forepoles along with wood forepoles. This section replaced the 40-lb rail which had formerly been used for the purpose. Having the 4-in. WF sections on hand, it was natural that our first experiments in steel sets involved their use. Later, the rolling of the 10-lb section was discontinued in favor of the much stronger 13-lb section, which is now standard for both legs and caps in areas of no particular weight, but which, none the less, require permanent support. Our experiments involved the use of the 10- and 13-lb sections as legs and 6- and 8-in. I beams, 16 and 23 lb per ft, respectively, as caps. Experience soon indicated that, if the ground were heavy enough, and the opening wide enough to require a cap stronger than 13-lb, the 8-in, 23-lb should be used, eliminating the 6-in. I beam. We now know that the 8-in. WF section of the same weight, which we propose to use in the future, is considerably stronger for the amount of money involved. Comparative Strengths: Tables I to IV giving strengths of several species of timbers as compared with the structural sections that we now use have been prepared in accordance with accepted practice. Experience indicates that failure due to compression perpendicular to the grain of the wood does not destroy the effectiveness of a wood set frequently enough to be a practical factor. Therefore, no table of these values is included.

Jan 1, 1951

By Tibor Stefansky, John E. Dorn

MOTT and Nabarro1-5 were first to illustrate the importance of the flexibility of dislocations in accounting for the strengthening that metals undergo due to the presence of internal-strain centers. Such strain-centers might arise from a number of causes such as radiation damage, the presence of semicoherent and coherent precipitates and clusters, as well as individually dispersed interstitial and misfit substitutional solute atoms. Each strain-center induces positive and negative shear stress fields on the slip planes of the surrounding alloy matrix. In order to effect plastic deformation, therefore, the alloy must be subjected to sufficiently high applied shear stresses to push dislocations past all such internal stress fields. If dislocations were inflexible and moved as rigid lines, they would be equally pushed and pulled by internal stress fields. At this extreme the strengthening would be vanishingly small. Dislocations, however, are not rigid; they are flexible and extensible. They wiggle between positive and negative strain-centers, thus increasing their line energy at the expense of their interaction energy with strain-centers. cottrel16 and Friedel7,8 have independently presented lucid reviews of the significance of the Mott-Nabarro dislocation-flexibility concept to the strain-center strengthening of alloys. Their analyses however were only semi-quantitative. There is evidence in the recent literature of renewed interest in a more rigorous analysis of flexibility. Thus, Gleiter9 and Gerald" have shown that the calculated strain-energy interaction between a dislocation and the stress fields of coherent precipitates can be seriously in error if the flexibility of the dislocation is not taken into account. This report will be concerned with a more detailed analysis of the problem based on the following approximations: 1) Although many types of strain-centers exist, the following analysis will be limited to the case of solute-atom strain-centers in fcc substitutional alloys. 2) To facilitate the analysis by avoiding statistical considerations, the strain-Centers are assumed to be in regular arrays on the slip plane. Although the quantitative results are somewhat dependent on the type of array that is assumed, the qualitative trends are similar for various arrays that were studied. 3) An adjustment of the results from those for square arrays to those for the more realistic case of a random distribution of strain-centers is accomplished by adopting the interesting statistical theory first introduced by Kochs,11,12 elaborated on by Dorn, Guyot, and stefansky,13 and analyzed by Foreman and Makin14 in their computerized experiments. 4) For simplicity the dislocation lines are taken to wiggle about their edge orientation and no correction is applied to their line energy for deviations from edge configurations or for the elastic interaction between segments of the now curved dislocation. It will be shown that for extremely low concentrations of atomic strain-centers the strengthening increases with the square root of their concentration. For slightly higher concentrations the strengthening rate becomes less rapid. At a critical concentration a maximum strength is obtained and a decrease in the strengthening takes place as the concentration of solute atoms is further increased. These trends are a direct consequence of dislocation flexibility. They arise from changes in the amplitude of the waviness of the dislocation line at the yield stress with solute atom concentration. Despite the simplifying assumptions that were made, the results agree qualitatively with appropriate experimental data. I) STRESS FIELDS ON SLIP PLANES Internal stresses are introduced in a lattice whenever a host atom of radius ro is replaced by another that has a different atomic radius. According to the classical theory of linear elasticity,15 the stress field about a solute atom at the origin of a spherical coordinate system is given by arr=-4G€(?_0)3 ffflfl ="W =2G€{t) f°rr^ro(l+e) UJ where G is the shear modulus of elasticity and Y, = ro(l + E) is the radius in situ, of the substituted atom. As shown by ~shelb~,&apos;~ this approximation assumes that the bulk modulus of elasticity of the substituted atom is identical with that of the host species. ~abarro&apos;~ suggested that the strain E can be deduced

Jan 1, 1970

By F. J. Haller

IN 1943, we found, in the new Mather operation, a very unusual and disappointing condition in the footwall rock where all of our main haulageways were to be located. With the exception of a few hundred feet out of the thousands then planned and since driven, all of the openings require support. In general, the ground is not particularly heavy, at least by our standards, but it must be supported and the back carefully covered. Also, our operations require rather wide plat openings (16 to 18 ft) and rather flat curves at the turn-outs, all of which adds to the problem. When this completely unforeseen condition was discovered, ordinary timbering was the only answer, because of the impossibility of obtaining adequate steel supplies in time due to war shortages. Then by the time steel supplies were obtained and a practice developed, we found ourselves with between four and five miles of main haulage drifts and plat openings of a permanent nature, all of which were supported by hardwood timber, some of which had already rotted to an unsafe degree. Also, our drifting program was adding some two miles per year to the above figure. F. J. HALLER, Member AIME, is Superintendent, Mather Mine, Cleveland-Cliffs Iron Co., Ishpeming, Mich. AIME Columbus Meeting, September 1949. TP 2840 A. Discussion (2 copies) may be sent to Transactions AIME before May 31, 1950. Manuscript received Aug. 22, 1949. Revision received Jan. 17, 1950. To give all of the details of our experiments, studies, and experiences would fill a large book, but we were satisfied that our organization had done an excellent job, starting from scratch. You can appreciate our surprise when we discovered that we had added very little to an existing record. Attention was called to a footnote in a copy of "Carnegie Pocket Companion" year 1923. The note read: "Full information as to uses of H-Beams is given in pamphlet entitled &apos;Steel Mine Timbers.&apos; " A search of our Engineering Library brought to light a pamphlet printed in 1911 showing extensive use of steel for this purpose. Except for welding in place of riveting, we have added very little to the designs in that book. We have, however, developed an experience which proves, at least to our own satisfaction, that steel mine supports pay off under the proper conditions. We are now convinced, in spite of the relatively high initial cost of materials, that steel sets, because of comparatively low installation cost, are actually cheaper than either treated or untreated wood sets, if they are properly designed and adapted. Several Sections in Use: Convenience guided our first experiments in steel sets, since for a number of years, we had used the 4-in. WF, 10 lb per ft section in 10-ft lengths as safety forepoles along with wood forepoles. This section replaced the 40-lb rail which had formerly been used for the purpose. Having the 4-in. WF sections on hand, it was natural that our first experiments in steel sets involved their use. Later, the rolling of the 10-lb section was discontinued in favor of the much stronger 13-lb section, which is now standard for both legs and caps in areas of no particular weight, but which, none the less, require permanent support. Our experiments involved the use of the 10- and 13-lb sections as legs and 6- and 8-in. I beams, 16 and 23 lb per ft, respectively, as caps. Experience soon indicated that, if the ground were heavy enough, and the opening wide enough to require a cap stronger than 13-lb, the 8-in, 23-lb should be used, eliminating the 6-in. I beam. We now know that the 8-in. WF section of the same weight, which we propose to use in the future, is considerably stronger for the amount of money involved. Comparative Strengths: Tables I to IV giving strengths of several species of timbers as compared with the structural sections that we now use have been prepared in accordance with accepted practice. Experience indicates that failure due to compression perpendicular to the grain of the wood does not destroy the effectiveness of a wood set frequently enough to be a practical factor. Therefore, no table of these values is included.

Jan 1, 1951

By L. Larson

SMELTERMEN in the copper industry know that punching the tuyeres of a copper converter is a difficult, disagreeable, and at times a hazardous job. Knowing this, many men in the industry have given serious consideration to punching by mechanical means. As evidence of such consideration, a great many patents have been issued covering various mechanical devices or machines for doing this task. In 1942, as war-created manpower shortages became more acute, it became increasingly difficult to get men to punch tuyeres. Faced with this situation at the McGill smelter, it was decided that an all-out effort should be made to develop some sort of a mechanical punching device. The various patents were studied over thoroughly but none of the devices seemed suitable, all were discarded and it was decided to develop one, using the ideas of the personnel at McGill. Initial test work indicated that a separate punching device should be attached to each tuyere. This meant that an adapter would have to be developed which would accommodate such a device; the adapter to be so constructed that it could be substituted for the regular Dyblie valve head, and be punched either by mechanical means or by hand. Also a method for quickly attaching or detaching the punching unit would have to be devised. If the punching unit was attached to the adapter, then the punch rod and tip would have to remain inside of and reciprocate within the tuyere pipe. This last requirement meant that the punching device, the adapter, the piston rod, and punch rod must be in perfect alignment. The whole arrangement thus would become an integral part of the converter and would rotate along with the tuyere line to all the positions required for converter operation. If the puncher was to rotate with the converter, there was also a problem of limited clearance. The construction of a device to meet all of these conditions imposed many problems. In the latter part of 1942, two pieces of equipment were constructed and tried out under test-stand conditions. Both of these devices were very crude, but test-stand operation indicated that progress was being made. Neither of the units was considered good enough to be attached to and tried out on a tuyere of an operating converter. In May 1943, work was started on another device and in August of that year it was attached to and actually punched a single tuyere of a converter on an experimental basis (fig. 1). This unit was essentially a cylinder 3 in. in diam and about 15 in. long inside. Valve ports were so located as to provide a 1-in. cushion on each end of the stroke. The cylinder ports were piped to a 3/4-in. four-way disk valve. High pressure air (90 psi) was delivered to the valve by means of a long hose, thus making it possible to supply air to the device at all operating positions of the converter. The forward and return punching strokes were accomplished by shifting the valve handle as required. With the 3/4-in. valve, stroke velocities from 15 to 18 fps were achieved. Punching with this experimental arrangement was carried on for some time, but many difficulties were encountered. The punch rod tips often stuck in the tuyere accretion, indicating that more energy of some sort was necessary to avoid sticking the punch rod. To overcome sticking, experiments continued with a speeded up unit and although progress was made, troubles of various kinds continued to appear. On this unit, piston cup seals passed the valve ports which proved to be of very poor construction. Also the piston, driven forward at approximately 28 fps, would often bottom metal to metal in the forward end of the cylinder causing both mechanical and operational trouble. Sometimes the punch rod and at other times the piston rod would break loose and be shot through the tuyere pipe into the converter. Bottoming and poor timing of valve reversal caused a bounce and a hesitation at the end of the forward stroke, with the result that the punch rod

Jan 1, 1951

By J. O. Brittain, N. R. Adsit

A number of zinc bicrystal specimens with the grain boundary loaded in simple shear were plustically deformed in creep in a vacuum at 200°C and under an argon atmosphere at 350°C. The results indicated that the amount of grain boundary sliding at a given time was controlled by the slip in the grains and was proportional to the resolved shear stress on the slip plane. Curves of grain boundary sliding vs time were found to be cyclic with no regular periodicity. ALTHOUGH grain boundary sliding (G.B.S.) has been investigated in a number of different types of tests on various materials there is substantial disagreement on the interpretation of the various observations. Gifkins1 has presented a comprehensive review of the subject of G.B.S. and fracture. He reports that the activation energy for high-temperature creep is equal to that for volume self-diffusion and that pure metals show less tendency towards intercrystalline fracture than alloys. Pure metals show appreciably greater grain boundary migration than alloys, and both grain boundary migration and grain boundary sliding follow the same general trend in time as plastic deformation during creep.&apos; While there have been a number of different mechanisms proposed to account for G.B.S., none of the models explains all the results. Since zinc has only one prominent slip system, it was hoped that experiments on G.B.S. in zinc bicrystals might enable us to separate the effect of grain boundary angle and the effect of matrix slip and thereby resolve at least one part of this complex phenomenon. EXPERIMENTAL PROCEDURE Bicrystals of pure zinc (99.99 pct) were grown by a Bridgeman technique in a furnace having a gradient of 20°C per in. The bicrystals were seeded to a desired orientation and grown in a split graphite mold which was 3/4 by 5/8 by 8 in. The mold was enclosed in a Pyrex tube and the tube was evacuated and then filled with a small amount of argon before it was placed in the furnace. The growth rates were 1/2 to I in. per hr for the bicrystals and 1/2 to 3 in. per hr for the single-crystal seeds. The longitudinal V notches served to hold the grain boundary in position during the growth process. A schematic rep- resentation of a specimen which had been cut with a jewelers saw from the bicrystals is shown in Fig. 1. All specimens of a series were cut from the same crystal, some of which were 7 in. in length. After specimen preparation the boundary was approximately 5/16 in. long and the V notches had a radius of 1/16 in. The boundaries were straight at a magnification of X100 with the exception of a few which had a gradual radius of curvature of greater than 3.2 in.-1. Laue back-reflection photograms were taken on the specimens to check the orientation of grains in the bicrystals. The method of relating the orientation of the two lattices is shown in Fig. 1, where 0 is the angle between normal to the boundary and the trace of the basal plane, is the angle in the boundary between the trace of the basal plane and a line parallel to the V notch, and x is the angle in the basal plane between the Burgers vector and the perpendicular to the grain boundary. After mechanical polishing the specimens were chemically polished.2 Subsequent to the polishing operation the specimens were encapsuled under a vacuum of better than 25 annealed at 340°C for 1 hr to remove the effects of this handling, and again chemically polished. Finally, fiduciary marks were scribed on the specimen using a micromanipulator. Creep tests, which were conducted in a modified Bausch apparatusS with the boundary loaded in simple shear, were run at a constant load (since the boundary area remained essentially constant this is approximately constant grain boundary stress). The temperature was controlled to ±1/4°C as measured on a semiprecision potentiometer with a calibrated thermocouple. The specimens were tested in a vacuum of better than 0.5 at 200°C and in purified argon at a pressure of 1/2 atm at 350°C. The op-

Jan 1, 1965

By Elmer Weber, W. M. Baldwin

Solid lead obeys a single parabolic weight increase vs. time law. In contrast, liquid lead undergoes three successive parabolic weight increases vs. time laws, the first of which has a low constant relative to the latter two. The conversion times for the change from one parabola to the next decrease with increasing temperature. IN recent reports on the subject,1,2 it was noted that zirconium and titanium scale in air by a complex mechanism. The scale first forming on the metal is protective to the extent that it gives a low constant, K, for Tammann&apos;s, and Pilling and Bedworth&apos;s parabolic equation: w² = Kt [1] relating weight increase, w, due to chemical reaction of the metal with the air, and time, t. After hundreds of hours of apparent stability in some cases the first scale yields to another that offers little protection to the metal. This transition from one scale to another, from a slow parabolic oxidation reaction to a fast one, was not due to impurities in the atmosphere or incidental effects (changing environment, etc.) but was a specific behavior of the metal itself, the transition occurring at definite times (dependent on temperature) and showing other reproducible traits. In view of this behavior how can long-time service behavior be predicted from short-time laboratory tests, not only in the case of these metals, but in any case? Certainly a systematic study of the type of scaling behavior described above—wherever it is found—would help to answer this question. The present paper is a report on the behavior as it is found in lead—the only metal to the authors&apos; knowledge for which the behavior has been described at all, if inadequately, for our present purpose.* At least four oxides of lead are known, of which one occurs in two allotropic forms. They are ß (red) tetragonal PbO stable up to 486°C;8 a (yellow) orthorhombic PbO stable from 486°C up to its dissociation temperature in air at about 2300°C;9 minium or Pb3O4 which from the dissociation pressure data given in Fig. 1 decomposes to PbO at 540°C in air; lead sesquioxide or Pb2O3,; and lead dioxide or PbO2 which, according to Fig. 1, decomposes in air at 400°C to minium. In view of the high dissociation temperature of PbO, lead will scale up to at least its boiling point. Further, it is known that oxygen is almost insoluble in liquid lead.&apos;V his implies a fair probability that an oxide scale would not dissolve in the molten metal and would afford the same protection to lead in the liquid state as in the solid. All of the oxides of lead for which specific gravity data are available are more voluminous than an equivalent weight of metal or a lower oxide from which they might form, hence the scales will be in compression. Lead oxides are known to be ductile, so it would be anticipated that they would form coherent nonporous scales. It is not surprising to learn, then, that both solid and liquid lead scale according to the Tammann, and Pilling and Bed-worth law.14,15 (Gruhl states that at 600°C and above lead oxidizes linearly with time because of "spitting" of the scale.) The parabolic constants K reported by various investigators3,14-16 are badly scattered, however, as shown in Fig. 2. The oxides formed on solid lead were described as being reddish-brown but were not chemically identified by Pilling and Bedworth.15 Gruhl&apos;s descripdin³ of the appearance of the scales On his liquid samples indicates that a (yellow orthorhombic) PbO is formed initially on the specimens but gives Way eventually—at least at temperatures below 486 °C— to .ß (red tetraunal) PbO, and that below 540°C minium—Pb3O4 :is firmed at an even later time as an overlay on either the red or yellow PbO. Fig. 3 is a graphical interpretation of Gruhl&apos;s description. Gruhl does not indicate any change in the parabolic scaling rate as yellow PbO converts to red. He does indicate that minium reduces the scaling rate, al-

Jan 1, 1953

By H. L. Hartman

The drop tester has proved an invaluable tool for the investigation of percussion drilling in the laboratory in "slow motion". It has allowed the process of rock penetration by impact to be studied a single blow at a time. In the present work, the relation of cratering to indexing has been determined under conditions simulating those in the bottom of the hole at atmospheric pressure. Indexed blows form craters which are influenced by others adjacent to them. Two unique effects are involved: (1) the provision of additional free faces in proximity to the point of impact and (2) the creation of subsurface damage by the previous blow(s). Both have a pronounced influence on the volume of rock removed per blow, which governs the rate of penetration in actual drilling. The emphasis in this study was placed on determining effects of index distance and impact energy on crater volume when blows were struck on a previorusly "drilled" or damaged surface, a situation most representative of down-hole conditions. The results indicated that (I) the optimum index distance on a damaged surface is greater than on a fresh, undamaged rock surface; (2) the volume of rock broken at optimum index distance is about the same for both surface conditions with die-shaped chisels but tends to be greater on a cratered surface with wedges; (3) the optimum index distance and maximum crater volume are proportional to the energy level; (4) at a given energy level, the volume of rock broken by dies generally exceeds that by wedges; and (5) maximum crater volume varies, approximately, inversely with width of die but is nearly independent of included angle of wedge. INTRODUCTION This is the third of a series l,2 of papers reporting on one phase of a continuing program of drilling research being conducted in the Rock Mechanics Laboratory at The Pennsylvania State U. The phase under consideration is crater geometry — blow energy relations in percussion drilling. While the previous papers have discussed mainly craters produced by single blows, indexed-blow studies are the subject of this paper. The basic mechanism of drilling under study here — that of penetration of a chisel-shaped bit subjected to impact — is the one employed in probably 90 per cent of all rock drilling in mining, percussion drilling. It also forms the fundamental action in nearly all oil well drilling with the so-called rotary (roller-bit) method. Here, the action is more complex, however, and may in actuality comprise rotary-percussion drilling. Certainly, the down-hole air and mud hammer drills, which superimpose percussion on rotation, belong in this latter category. In any event, impact blows constitute one of the principal mechanisms in the vast majority of drilling, mining or petroleum, and it is essential in drilling research to study percussion in all its basic aspects. Percussion drilling can be simulated in the laboratory by means of an impact drop tester. Striking one blow at a time with chisel-shaped bits, the drop tester permits study of most of the parameters in the drilling process except blow frequency and the interrelationship of certain variables. Single-blow craters, the simplest to produce, allow the determination of basic relationships, such as volume vs blow energy; while indexed craters most closely resemble the action in real drilling and provide data for the establishment of optimum operating criteria. Indexed-blow craters are those which are influenced by others in proximity. The simplest case to visualize, and the one studied in detail here, is that in which a given crater is formed adjacent and parallel to a previous crater, such that the second crater breaks into the first. A more complex situation usually exists downhole, where indexing is achieved by rotation of a radial-winged or rolling-cutter bit. But, admittedly, the phenomenon of indexing is more likely to be understood eventually if it is first studied in its simplest form, that related to parallel craters. Limited research has been conducted on indexed blows. The most complete study was that by Simon, 3,4 who proposed universal indexing curves to relate the important variables. His work, however, was conducted entirely with rows of craters formed on a