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By Thomas A. Steven

Most mineralized areas in the central San Juan Mountains, Colorado, are associated with the youngest subsidence structures in a large volcanic cauldron complex that formed concurrently with eruption of the surrounding ash-flow field. Two local types have been recognized: (1) fissure-vein deposits along faults characterized by relatively late movement, and (2) hydrothermally altered and mineralized areas associated with postsubsidence Fisher Quartz Latite centers. The first type has provided most production in the past; the potential of the second type has yet to be adequately tested.

Jan 1, 1968

By F. William Bloecher, William B. Plank

CURRENTLY 12,892 students are enrolled in the mineral engineering schools of the United States and Canada, marking an all-time record high for these schools. It shows a remarkably rapid recovery from the effects of World War II. Enrollment in all the other engineering branches has also increased but not so rapidly as in the mineral engineering branch. Almost all the data in this report are from the eighth questionnaire study of the mineral engineering schools made, as formerly, under the auspices of the Mineral Industry Education Division of the AIME. Every school is represented in the data, for which the authors thank the deans and professors who supplied the information. For this reason, the data of all the studies are comparable, an achievement not always possible in endeavors of this kind. For comparison with the general engineering enrollment situation, data are included from the January 1947 issue of the Journal of Engineering Education.

Jan 1, 1947

By Robert Glass Cleland

IN gathering material for this book, I have made extensive use of the archives of Phelps Dodge, contemporary news- papers, and a wide range of secondary sources. Two manuscripts-one on the history of Phelps Dodge by Arthur Train, Jr., and John L. Lawler, the other a biography of William E. Dodge by Richard Lowitt-have been of the greatest value. I owe a particular debt to the authors whose names I have just mentioned. I have also gathered important information and obtained revealing points of view from conversations with many people. Personal visits to the company's mines and plants added knowledge and understanding that nothing else was able to supply. I am greatly obligated to the officers of the company, especially to Mr. Louis S. Cates, chairman of the board of directors, Mr. Robert G. Page, president, Mr. George R. Drysdale, vice-president of Phelps Dodge Corporation, and Mr. Walter C. Bennett, president of Phelps Dodge Refining Corporation, for their co-operation and assistance. Mr. Wylie Brown, former president of Phelps Dodge Copper Products Corporation, also supplied valuable data and deeply appreciated hospitality. In my visits to the Phelps Dodge properties, company representatives extended every hospitality and placed at

Jan 1, 1952

By D. L. Archer, W. W. Owens

Conventional waterflooding often is uneconomic in highly fractured reservoirs because of the gross bypassing of the reservoir oil by injected water. Imbibition and pressure pulse flooding have been used in at least one fractured reservoir in an attempt to achieve better oil recovery performance. This paper presents the results of laboratory flow tests conducted on large cores to evaluate the possible applicability of these methods (particularly pressure pulse flooding) to different types of reservoir systems. Test data were obtained on both water-wet and oil-wet systems, and on systems having two widely different levels of compressibility and flow capacity. Results indicate that pressure pulse recoveries from fractured reservoirs will likely not exceed 5 to 10 per cent pore space with maximum response achieved during the first pulse cycle. Improved recovery by this method is possible from both oil-wet and water-wet reservoirs. Comparable saturation distributions during imbibition and pressure pulse production suggest that an initial pressure pulse cycle to speed production response would not interfere with subsequent imbibition flooding in water-wet reservoirs. INTRODUCTION There is a steady increase in the number of fluid injection projects being initiated each year to improve oil and gas recovery over that obtained by primary production mechanisms. Experience gained in different geographical areas and with different recovery methods is teaching that reservoir anatomy is one of the more important factors controlling the success or failure of such projects. Fractured formations appear to be the rule rather than the exception, especially in carbonate reservoirs. Conventional methods of fluid injection, whether it is waterflooding, gas injection or miscible flooding, have limited applicability to highly fractured reservoirs because of the severe bypassing of reservoir fluids. The result is early breakthrough of the injected fluid and rapidly increasing ratios of injected to in-place fluid with an undesirable effect on return on investment. Thus, innovations to conventional methods must be developed if recovery from fractured reservoirs is to be optimized. One new method proposed for application to highly fractured reservoirs is pressure pulse waterflooding. Although pressure pulsing with gas has been suggested' and rested in at least one reservoir; the Sohio Oil Co. is generally credited with the development and testing of pressure pulsing in conjunction with waterflooding. Publications" of Sohio's waterflood operations in the Spra-berry Trend indicate that the idea for pressure pulse flooding evolved from a critical analysis of the disappointing early performance of their flood initiated in a portion of the trend in April, 1961. This flood was planned to take advtantage of imbibiltion and high pressure gradients across the reservoir matrix blocks (unfractured Mocks of the reservoir rock which are visualized to be generally surrounded 'by the fracture system) evaluated in pilot tests by the Atlantic Richfield Co.5 and Humble Oil & Refining Co.' However, the early recovery and pressure performance of this flood indicalted that high pressure gradients induced between the fracture system and the centers of the matrix blocks were forcing water into the periphery of the blocks and temporarily interfering with the counter-current flow of oil due to imbibition. Fill-up in the blocks was occurring with re-solution of the free gas phase as pressures climbed above the original reservoir bubble point. It appeared that cessation of water injection to permit the capillary forces to become dominant and that expansion of the rock and its contained fluids during pressure reduction might aid in expulsion of oil from the rock matrix into the fractures. Subsequent production performance. aflter cessation of injection, proved this hypotheslis correct. Thus, pressure pulse waterflooding was born. Pressure pulse flooding appears to have several advan'tages over imbibition type flooding in highly fractured reservoirs. First, all wells may be used for water injection which should hasten fill-up and achieve a more rapid increase in reservoir pressure. Second, because of increased injection pressures and rates, flooding gradients will force water into the reservoir matrix more rapidly than would be achieved by imbibition alone. Third, during the pressure depletion cycle of the flood, the compressibility of the system, which has been increased by resolution of the free gas phase, provides energy for the displacement of oil at a rate greater than would correspond to countercurrent flow during imbibition. Fourth, during depletion all wells may be put on production, thus contributing to higher oil withdrawal rates on a reservoir-wide basis. One possible disadvantage of pressure pulse flooding as compared to imbibition floodling, however, is that the outer periphery of each matrix block is flooded to a residual or near residual oil saturation during the Water lnjection stage. This zone of reduced permeability to oil m'ay offer greater restriction to the production of

Jan 1, 1967

E. B. WILSON, Scranton, Pa. (written 'discussion *).-Prof. Young's paper shows another application of electricity in solving problems in coal mining, and suggests that it may be possible to utilize the data he has collected in developing an electric firedamp detector. If electric lamps are to be adopted in gassy coal mines, the use of an electric firedamp detector becomes almost imperative, for safety lamps and electric lamps in the same mine are not always conducive to safety, and Liveings electric firedamp detector, is too cumbersome to meet with general approval. Three well understood facts are verified in a new way by Prof. Young's experiments: - 1. The temperature at which methane ignites. 2. The more inflammable gas present in an atmosphere, the hotter will be the flame, and the longer the cap in a safety lamp. 3. As the temperature at the source of ignition varies, the length of the gas-cap flame varies. Prof. H. B. Dixon collaborating with Mr. H. F. Coward, some years ago, made experiments on the ignition of various gases to find the tem-perature of their kindling points.1 From the results of their experiments, the writer has culled the ignition temperatures of some hydrocarbon gases, and has tabulated them with other data, in Table 1.

Jan 10, 1919

By John V. Beall

One Sunday night last month the phone rang and it was George Schenck from Penn State. How would we like to see a big scrap operation, he wanted to know. A few days later we were on the Connecticut turnpike headed for New Haven to visit a large scrap operation, M. Schiavone and Sons. George had a large clam basket in the back which he explained was for collecting trophies. The car shredder, he said, turns out some fancy metal shapes. In fact, they have gained a certain acceptance as objets d’art among George's friends and relatives. He thinks there may be a small, but possibly lucrative secondary market for shredded cars in the art world if the idea is imaginatively promoted. On the way to New Haven we received a briefing on the scrap industry. The scrap business grew from humble beginnings. Mostly it was started by a few immigrant Jews who collected junk in hand- or horse-drawn carts. The fortunate one might even have had a truck. Before proceeding further, we hasten to point out that the word "junk" is strictly taboo among scrap people, who prefer to refer to their industry as the "secondary metals industry."

Jan 1, 1970

By Luther Lennox

DURING the last few years, one of the great problems in the milling of all ores has been that of crushing. This subject involves not merely the cost of the operation, but also the selection of the proper degree and character of crushing to yield the best metallurgical results on the given ore. Considering the diversity of machinery, one is led to wonder at the variety of crushing methods employed, even when realizing that metallurgy demands varying products. In an attempt to investigate the relative crushing resistances of a number of ores now being milled in this country and Alaska, the management of the Portland mills requested samples of average mill-run of ore from various companies. The request met with a ready response, indicating the desire of all operators to gain information on the subject. The difficulties involved in this investigation were numerous, lack of time for outside problems during this strenuous period being a serious one. Also, we were unable, in the time, to obtain a correct 150-mesh . screen; in the screen analyses tabulated and plotted herewith, the 150 mesh screen was used merely to protect the 200-mesh screen, not to ascertain points on the curves.

Jan 8, 1918

By George B. Clark

THE geological data emphasized so successfully in prospecting for new deposits, that is, structural controls, strength of solutions, and type of mineralization, are basically those required for successful exploitation. In the mining of newly discovered deposits the most economical methods should be employed as early as possible to keep the overall cost per unit produced at a minimum and to permit maximum extraction of valuable minerals. A crucial question is: How can geological data be translated into useful quantitative results which will aid in achieving this end? H. E. McKinistry1 has suggested that a solution may be reached in one of two ways: 1-the usual approach, use of judgment based on experience; or 2-mathematical calculations and tests on models, both subject to certain limitations. He also suggests that in addition to better use of geology more case data and theoretical data are needed on which to base sound judgment. Further research, therefore, is necessary. Perhaps in this field the emphasis should be on more specialization in mining methods and ground movement by men with thorough training in physics, engineering, geology, and underground mining. These specialists would be equipped to point out the most economical and scientific methods of exploitation.

Jan 8, 1954

By C. Alstetter, V. Kerlins

By using alloys with subzero Ms temperatures, this investigation demonstrates that the amount of decomposition of martensite during the quench from austenite may be considerable and especially so in specimens of large cross -sections and high Ms temperatures. The activation energy for decomposition as measured dilutometrically is PREVTOUS investigations of the initial decomposition of Fe-C system martensite have invariably been limited to alloys having M, temperatures above a function of the amount of transformation which has taken place. The amount of transformation is a linear finction of log time. A correction term to the activation energy is derived for dilatometric measurements in which no end-point of the transformation is detected. room temperature. In such alloys the martensite is tempered during the quench to an extent dictated by the quench rate and temperature of formation. This tempering, called quench-tempering, Q-tempering, self-tempering, or auto-tempering, although frequently acknowledged, has not been studied or treated quantitatively. To do so one should obtain absolutely untempered martensite and study its decomposition. This as-formed martensite could be obtained either by extremely rapid quenching, requiring very thin specimens, or by lowering the martensite formation temperature range. The second alternative is more effective, because

Jan 1, 1963

By S. Skowronski, K. W. McComas

Page Purpose of investigation.....................'. 354 Details of experiments........................ 357 Experiment Series No. 1, melting copper containing chlorine under carbon dioxide............................... 358 Experiment Series No. 2, melting hydro-electric cathode copper drillings under air................................ 362 Experiment Series No. 3, melting hydro-electric cathode copper drillings under furnace gases............................ 363 Summary.............................. 364 Purpose of Investigation Since cuprous chloride melts at 418' C., boils at 954' C. to 1032' C.,' and is known to be volatile at a much lower temperature, the presence of chlorine in any form in or on copper to be melted has always been looked upon by copper refiners as a possible source of serious copper loss. Although this fact has been known for some time, the copper literature contains little or no information regarding it and the field seems never to have been properly investigated from a metallurgical standpoint. According to Greenawalt,2 cupric chloride, CuCl2, when ignited gives cuprous chloride; therefore cuprous chloride is always formed when copper enters into reaction with chlorine at a high temperature. Cuprous chloride melts somewhat below a dull red heat, and does not volatilize in closed vessels, even if strongly heated, but if heated in the air it goes off as a white vapor, Hofman3 gives the melting point of cuprous chloride

Jan 1, 1919

By P. G. Linder

The mechanical concentration of ores has not attained any considerable extent in Sweden, by reason of a scarcity of ores calling for this kind of treatment. Of rich iron-ores there is still an abundant supply; and magnetic concentration, which in the future undoubtedly will become of great importance, not being as yet demanded by necessity, has not advanced beyond a few experiments. At the copper-mines mechanical concentration has been superseded by chemical processes; the lead mines are worked out; and it is (with one exception) only the mines producing blende, or blende and galena intimately mixed, that have adopted mechanical methods for enriching their low-grade ores. While the concentrating-plants in Sweden are few and their output is comparatively insignificant, the methods employed, the general features of the work and the results obtained under extremely unfavorable conditions, may offer some points of interest to persons who are engaged in this branch of industry and have similar problems to deal with. Before going into a detailed description of the several plants, I will offer a few remarks that hold good for all of them and constitute a general review of Swedish concentration and its conditions. At all the works the ore to be treated is a mixture of blende and

Jan 1, 1895

By E. S. Machlin, C. W. Chen

RECENTLY Chen and Machlin' proposed a mechanism for intercrystalline cracking in metals during high-temperature stressing. According to this mechanism the formation of voids at grain boundaries is primarily responsible for intercrystalline cracking. A model has been provided to demonstrate the initiation of submicroscopic cracks and voids at jogs of grain boundaries where grain boundary sliding is inhibited. Submicroscopic cracks can grow as a result of either further grain boundary sliding or localized tensile stress. In the former case, it is believed that grain boundary sliding produces more voids which link together to produce macroscopic cracks and which may lead to the eventual failure of the metal. Concurrently, Nield and Quarrell2 reported their interesting results obtained in a systematic investigation of intercrystalline cracking in two aluminum alloys under various creep conditions. Their observations are generally in agreement with the above mechanism, especially the conclusion that voids are formed as a direct consequence of grain boundary sliding. On the basis of the volume fraction occupied by voids, they could find no confirmation of vacancy condensation as the mechanism for void growth. Furthermore, an important feature of intercrystalline cracking has been likewise pointed out by them that the majority of cracks are not formed at grain corners. Nield and Quarrel1 meanwhile emphasized the importance of grain boundary migration by designating it as one of two main processes operative in the mechanism of crack formation during creep. The designation seems unnecessary because overemphasis of grain boundary migration only complicates the mechanism of void formation. There are two reasons which militate against the inclusion of grain boundary migration in the mechanism of void formation. In the first place, the formation of intercrystalline voids per se does not require grain boundary migration. Secondly, in addition to grain boundary migration, void formation may be minimized by any other process such as plastic deformation which is capable of relieving localized stresses around jogs. Chang and Grant3 have shown that intercrystalline cracking is prevented in aluminum by lattice bending in high stress regions. The influential role played by grain boundary migration in creep has also been realized in our studies. In several cases, voids did not appear at all in grain boundaries whenever grain boundary migration took place prominently during creep. The purpose of this paper is to discuss the effect of grain boundary migration on the formation of intercrystalline voids and other related rupture properties. Experimental evidence indicates that in an unstable grain structure void formation may be markedly modified by structural changes. The abnormally high ductility and the transcrystalline mode of fracture observed in copper at elevated temperatures reveals that effective grain boundary migration minimizes void formation. Grain boundary migration has long been known as a common high-temperature phenomenon in metals with the grain configuration in a nonequilibrium state. Its effect on ductility and mode of fracture has not been recognized until recently.4 Since the introduction of the term "Equicohesive Temperature," the conventional belief has been that below the equicohesive temperature the ductility of metals increases moderately with decreasing temperature until the ductile-to-brittle transition temperature of fracture is reached. In this temperature range, metals fracture in a ductile mode with a "cup-and-cone" fracture surface. Above the equicohesive temperature, ductility remains invariably low and decreases slightly with increasing temperature. The mode of fracture is strictly brittle and intercrystalline. Typical examples have been shown for a brass and copper in Fig. 1 and 9, respectively, in the paper by Greenwood, Miller, and Suiter.5 The observation in the upper temperature range that ductility of metals is low and insensitive to temperature may be explained in terms of void formation at grain boundaries. It is also in accordance with the findings of McLean6 and Fazen, Sherby, and Dorn7

Jan 1, 1961

By M. Cohen, R. J. Teitel

There is considerable interest in beryllium because of its low density (1.84 g per cu cm), high modulus of elasticity (40 X 106 psi), high melting point (1280°C), and special nuclear characteristics. Moreover, it has fair resistance to corrosion and oxidation. However, the purest beryllium known to the authors is relatively brittle at room temperature, and cannot be fabricated readily. The search for improved properties leads naturally to investigations of beryllium alloys and the phase relationships upon which they are based. The present paper is concerned with the alloys of beryllium and iron, primarily from the standpoint of the equilibrium diagram. Iron was selected (1) because of its all-round importance in metallurgy, and (2) because the beryllium-iron system is known to be quite complex. The most recent diagram in the literature is that of Gaev and Sokolov,' and covers only the iron-rich end up to 16 wt pct beryllium. Beryllium markedly restricts the austenitic field, closing the gamma loop at about 0.4 wt pct (3 at. pct). On the other hand, beryllium is soluble in a-ferrite up to a maximum of 7.5 wt pct (34 at. pct) at the eutectic temperature of 1160"C. The eutectic composition lies at 10 wt pct beryllium (42 at. pct) and corresponds to a mixture of or and FeBez (called j3 in the present paper). The solid solubility of beryllium in the a phase decreases with decreasing temperature, and makes precipitation-hardening possible. These findings substantiate the earlier work of Oester-held,2 Wever and Mueller3 and Laissus.4 In addition to the FeBe2 (ß) mentioned above, Misch6 has reported on FeBes, and indicated evidence for another compound containing still more beryllium. A preliminary diagram by Gordon,5 not hitherto published, is given in Fig 1. Besides the phases previously named, there are shown a solid solution of extended range (e), a compound of limited solubility (t), and a high temperature phase (7). Beryllium is designated as 8. The t field contains the compound composition FeBea, and the f phase undoubtedly corresponds to the beryllium-rich compound found by Misch.6 The region around the { phase was proposed by R. J. Teitel based on Gordon's data. The details of the diagram are self-explanatory. It was the unusual complexity of this system that prompted the authors to undertake the present studies. By the same token, more emphasis was placed on the beryllium-rich than the iron-rich end of the diagram. Exprimental Details RAW MATERIALS The beryllium employed in this investigation was one of the purest grades available. Its chemical analysis after vacuum melting is given in Table 1. The metal assayed 99.4 wt pct beryllium. Vacuum melted electrolytic iron of purity shown in Table 1 was the source of iron.

Jan 1, 1950

By Rollin E. Hook, Attwell M. Adair

The yield and fracture behavior of recrystallized chromiztm have been studied in order to gain an understanding of the recrystallization embrittlement-rheotropic recovery phenomenon. The duc tile-brittle tensile transition temperature of recrystallized chromium was found to vary from 225 ° to -80°C as the ratio of specimen diameter/mean planar grain size decreased. The applicability of this observation to other bcc metals is briefly discussed. Brittle fracture in recrystallized chromium was found to be initiated predominately from intercrystalline rupture nuclei. Single crystals exhibit a high degree of ductility at 23 "C. The experimental data indicate that grain boundaries play a significant part in the yield and fracture behavim. Pres training significantly reduces the transition temperature, and high temperature aging does not result in re-embrittle-ment until complete recovery or re crystallization occurs. SEVERAL theories have been used to explain the recrystallization embrittlement-rheotropic recovery phenomenon in chromium. Wain, Henderson, and ohnstone' propose a Cottrell dislocation locking mechanism due to nitrogen, and Weaver and Gross and weaver 3 propose a strain-induced precipitation mechanism involving a chromium nitride precipitate. The researches of many investigators seem to leave little doubt that brittleness in chromium is promoted by interstitial impurities. Smith and seybolt4 have shown that the ductile-brittle transition temperature is lowered as the interstitial content is reduced. weaver3 provides evidence for a 150°C reduction in the tensile transition temperature as the nitrogen content is reduced from 20 to 5 ppm. Maykuth and affee' have suggested that the amount and orientation of grain boundary impurities may be responsible for the brittle nature of recrystallized chromium. This suggestion was based on their findings that wrought iodide chromium possessing a fiberous grain structure is ductile in tension at room temperature while a recrystallized grain structure is completely brittle. Previous investigations have not studied this phenomenon sufficiently to determine its cause. Perhaps this has been largely due to previous experimental findings that brittle fracture observed in chromium has been almost entirely transgranular.' In addition McNeil and imb,' who investigated coarse-grained as-cast chromium, describe the point of initiation of fracture as cleavage, close to the (100) plane, near or at grain bound-daries, or at included particles or voids. However, Hook, Adair, and ipsitt found that fracture in coarse-grained recrystallized chromium is initiated by intergranular rupture and then propagates nearly entirely by cleavage. This result, together with their finding that room temperature ductility in bending is observed for single crystals and coarse-grained polycrystalline specimens for which the number of grains through the specimen diameter is small, suggests that grain boundaries may play an important role in the brittle behavior of chromium. The recrystallization embrittlement problem can be resolved into two questions. These are, whether the controlling mechanism is predominately one of crack initiation or crack propagation, and whether brittle fracture is initiated predominately by slip or twin induced intergranular rupture or by cleavage. The following research was designed to study the role of grain boundaries on the brittle fracture of chromium in an effort to resolve these questions. EXPERIMENTAL PROCEDURES, RESULTS, AND DISCUSSION General Procedure. All tensile specimens (except 0.04 in. diam wires) were prepared from 1/4 in. diam swaged rod fabricated from one ingot. Details of fabrication are given elewhere. The results of impurity analysis for the swaged rod and for the

Jan 1, 1963

By R. E. Holmes, T. W. Leland

The solution to the unsteady-state mass- and heat-transfer equations describing the adsorption of a dilute component from a gas stream flowing through a packed bed is readily applicable to the design of hydrocarbon recovery units. The solution to these equations depends on the assumption of a linear equilibrium equation to relate concentrations on the surface to concentrations in the gas. This assumption is shown to be justifiable for components which are very dilute in the gas stream. This approach permits the prediction of the effects of bed shape and size, cycle time, and gas mass velocity on the recovery of each component. It also allows the time and gas flow rate needed for regeneration to be determined. The equations involve a constant for each component and another constant characterized by the type of adsorbent. These constants must be evaluated from operating data. Values of these constants determined for silica gel are presented. This paper points out the type of experitrrental data needed for a thorough design of hydrocarbon adsorption units. INTRODUCTION The growing importance of adsorption processes to recover hydrocarbons from natural-gas streams has created an urgent need for better methods to design and predict the performance of these processes. Since the original use of solid adsorbents in natural-gas processing was for dehydration, most of the current design methods for hydrocarbon recovery re extensions of those developed earlier for dehydration. These methods are based on an adsorptivity or bed loading factor defined as the amount of a particular component adsorbed per unit weight or per unit volume of the packed bed. The recovery of a given component is then expressed as an empirical function of its adsorptivity on a given adsorbent. In spite of the simplicity and initial utility of these methods, they are not completely satisfactory in that they do not predict the effect of the dimensions of the bed in relation to flow rate and cycle time, and do not predict the distribution of various components along the length of the bed. It is possible, however, to make a considerable improvement in the design of these processes by applying the basic equations of mass and heat transfer applicable to gases containing small concentrations of adsorbing components flowing through granular beds. These equations have been developed and solved by Anzelius,' Furnas,% nd Hougen and Marshall." where G = mass velocity of the inert constituents (assumed to be methane), lb/hr-sq ft, y = weight of an adsorbing component in the gas per unit weight of inert, lb of a given constituent per lb of methane, x = bed length, ft, p, = packed bed density, lb/cu ft, P, = gas density, Ib/cu ft, f = void fraction in the bed, t = time, hours, and w = weight of a given component adsorbed per unit weight of adsorbate free solid, Ib/lb pure adsorbent. The term on the left side of Eq. 1 represents the flow rate per unit bed volume of a component entering less the flow rate per unit bed volume of that component leaving the differential bed length. The terms on the right side represent, respectively, the accumulation rates per unit bed volume on the solid and in the gas phase within the differential bed section. The last term is negligible for this application since pgfv is quite small in comparison with p, and G. The partial differential is determined by the mass-transfer rate between gas and solid in the differential section.

By C. H. Li, J. A. Sarteli, W. Bonfield

The stress to cause a permanent micros train of 2 x 10-6 in. per in. (defined as the microscopic yield stress) in beryllium is found to be very sensitive to surface condition. The initiation of plastic flow in as-machined specimens, which contain a high density of twins and large residual compressive stresses to a depth of about 0.010 in. from the surface, occurs by the nucleation of slip from high stress fields around twin tips in the surface layers. Removal of the damaged surface layers by chemical polishing results in an appreciable increase in the microscopic yield stress, which is attributed to the remoual of stress raising twins rather than to the release of residual stresses. IT is well known that the macroscopic mechanical properties of beryllium are very sensitive to the nature of its surface finish. Matthews and coworkers1 have shown that the tensile strength of rolled beryllium sheet can be considerably enhanced by chemical polishing, presumably due to the removal of the high concentration of notches, twins, and large residual compressive stresses normally found in the surface layers of ground specimens. There was no similar effect of surface condition on the macroscopic yield stress (the stress to produce 0.2 pct strain), a point to which we shall return. To date there have been no extensive studies on the effect of surface condition on the microstrain region of beryllium. Recent measurements2 of the stress to cause a permanent microstrain of the order of 10-6 in. per in. on machined hot pressed QMV beryllium, gave values ranging from about 600 to 3500 psi. Reasons for the considerable scatter in the results were not discussed. In this paper, we wish to show that the microstrain region of polycrystalline beryllium is, in fact, very sensitive to surface condition. The stress to cause a permanent strain of 2 x 10-6 in. per in. which for convenience we will refer to as the microscopic yield stress, can be increased by almost a factor of 2 by minimizing the amount of surface damage. The variation of microscopic yield stress is attributed to the presence of twins in the surface layers, rather than to residual compressive stresses. EXPERIMENTAL PROCEDURE The starting material for this investigation was commercial purity hot pressed QMV beryllium, with an average grain size of about 20 . The effects of surface treatment were assessed by comparing the microstructure with residual stress measurements and microstrain properties. Specimens were prepared for metallographic examination by wet grinding with 240, 400, and 600 papers, followed by polishing with a suspension of fine alumina in warm 20 pct oxalic acid. After this treatment, the surface could be examined, either in the unetched condition with polarized light, or after etching in 2 pct hydrofluoric or boiling 20 pct oxalic acid with normal light. Thin films of beryllium suitable for electron transmission study were prepared from bulk specimens by chemical polishing with hydrofluoric and phosphoric acids, and were examined in an RCA-EMU-3 electron microscope. Residual stress measurements were made by a procedure similar to that of Treuting and Read.3 Specimens 4.0 in. by 0.625 in. by 0.080 in. were prepared by three different machining procedures, namely: turning, grinding, and sawing, in order to introduce different levels of residual stresses. An electrical resistance strain gage was attached to one side of the specimen, and that surface was then protected by an acid-resistant enamel, while the opposite surface was removed by etching approximately one thousandth of an inch at a time. The change in specimen curvature in the longitudinal direction was noted and the residual stress was calculated by the following formula:

Jan 1, 1963

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent investigations1. a data on relative grain boundary energies in silicon iron have been obtained. The present investigation is a continuation of this work along similar lines for the purpose of obtaining additional information on boundary energies. One aim has been to extend the data for a (110) series, which was formerly studied,' to small differences in orientation, since a recent theory3,4 based on a dislocation model of grain boundaries predicts a E. ? (A-ln ? )* form of energy curve for small differences in orientation. Another aim has been to provide data for a (100) series—all grains having (100) planes parallel with the surface of sheet speci-mens—and to compare the results with the predicted form of energy curve. Finally, information on the nature of approach to equilibrium conditions was to be obtained through observations on the movements of grain boundaries. Recently published papers2,3,5 have treated the mathematical problem of expressing equilibrium conditions for grain boundaries for the general case when boundary energy depends upon boundary orientation. The equilibrium equations, which relate equilibrium angles and grain boundary -free energies, contain additional terms that express the variation of energy with boundary rotation. It has been necessary in the present investigation, however, to neglect these additional terms since no data for their evaluation were available. Dropping the additional terms leads to the following approximate equations which were used: E12/sin ?3 = E18/sin?2 =E28/sin?1 or those of the form: E28 + E13 cos ?3 + E12 cos ?2 = 0 Experimental Procedure Except for sample F1, all specimens were made from two lots of silicon iron called C and L respectively. The compositions of these are listed in table I. In the preparation of 12 three-grain specimens for the present investigation, a controlled grain growth technique, which has been described previously,' was used. After preparation, the specimens were notched at the boundaries to shorten them as a means of providing more rapid approach to equilibrium in the anneals. Initial grain boundary angles were determined from micrographs taken at X500. Seven anneals, totaling about two days at 1300°C and two to four days at 1400°C, were run in an atmosphere of pure dry argon as described in a previous paper.' Boundary changes generally could be followed without metallographic surface preparation, because thermal etching occurred during the anneals. These observations indicated angle changes of as much as 35" in some instances, with the major changes occurring during the first anneal. Annealing was discontinued when the angles reached stationary values. Fig. 1 gives a schematic diagram for purposes of defining crystallographic and boundary directions for three grains with common plane parallel with the sheet. Differences in orientations (expressed by A) are the angles between [00l] directions. They can be calculated with the aid of the ?'s. The grain boundary angles can be calculated from the w'S. Results Results are given in table 11. Types of crystal-lographic planes refer to those parallel with the sheet. Orientations are given in terms of [00l] direc-tions as shown in fig. 1. Except for grain 3 of specimen H6, which was unintentionally tilted 7" out of a (100) plane, all grains generally were within 1" or 2" of the plane specified. The directions of boundaries were measured generally to within 1" on both upper and lower surfaces, and the average direc- tions were determined for use in calculating the grain boundary angles. Variations in grain boundary directions refer to deviations from average directions. Boundaries near the junction point for all specimens generally were very close to perpendicu-

Jan 1, 1951

By H. Kurushima, S. Tsunoda

An investigation of the hydrometallurgy of Cu-Zn concentrates by The Dowa Mining Co. of Japan is described and a detailed flowsheet of the Kosaka hydro-metallurgical plant is given. Sufficient operating experience has shown that the Dorrco FluoSolids system has proven successful for recovery of both zinc and copper by roasting in a fluidized bed. At present, 2400 metric tons of concentrates per month are being treated and recoveries of 93 pct Cu and 65 pct Zn are being effected. A SURVEY of the Japanese chemical industry in 1949 revealed, among other things, that sulphur-bearing blast furnace gas from the Kosaka smelter of The Dowa Mining Co. Ltd., Kosaka, Japan, was being exhausted to the atmosphere as waste. In addition, it was costing that company an average of ten million yen ($28,000) annually for damages to the surrounding property caused by the sulphur dioxide in the gas. It was recommended by this survey that the gas be utilized for the production of sulphuric acid by the contact process. Mr. Kurushima visited the United States in May 1950 to investigate the engineering, construction, and operation of a contact acid plant. Any acid produced at Kosaka would necessarily have to be 98 pct H,SO, to prevent corrosion in railroad tank cars transporting it to the point of use. However, the production of 98 pct acid requires constant volume and SO, content of the gas. As the converter gas at Kosaka fluctuates in both volume and quality, it was decided to evaluate the smelting process with relation to other methods of recovery. This evaluation revealed a relatively new type of roaster, the Dorrco FluoSolids reactor, which was reported to be capable of roasting the copper sulphide concentrate in an excess of air with the production of an SO1 gas strong enough for acid production and a water-soluble copper sulphate calcine. The copper sulphate then could be leached from the roasted ore and electrolytic copper recovered from the leach solution in much the same manner as practiced by the Chile Exploration CO. for treating naturally occuring copper sulphate ores. Use of a reactor of this type would eliminate the need for a blast furnace and converter and, in addition, would effect savings in labor and fuel. The Kosaka ore is a microscopically fine mixture of copper, zinc, and lead sulphides. The lead and a small amount of the barite present can be separated by flotation, but any separation of copper and zinc proved extremely difficult. In blast furnace operation at Kosaka, zinc had been slagged off until a stockpile of about 12,000,000 tons containing 5 pct Zn had been accumulated. Mr. Kurushima felt that if any of the zinc in the concentrate was sulphat-ized and leached with the copper, it also could be recovered electrolytically. The Dorr Co., sponsors of fluidization technique in the metallurgical field, suggested that sulphate roasting be tested out on a laboratory scale and that, if successful, a commercial Dorrco FluoSolids system be constructed. They indicated that the results from such laboratory tests could be transposed to a commercial scale without pilot planting the roasting operation. It was therefore decided to send samples of flotation concentrate to the West-port Mill, laboratories of The Dorr Co., for testing. The objective of Mr. Kurushima's visit to the United States thus had changed from investigation of sulphuric acid plants to a fundamental examination of the hydrometallurgy of copper and zinc. Testing Program In February 1951, Mr. Tsunoda went to the United States to witness the application of the FluoSolids system to sulphate roasting at The Dorr

Jan 1, 1956

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst' and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick's3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,' and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"' have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol' and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.'' Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1'

Jan 1, 1961

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970