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By T. Leser, A. W. Jenike

The problems of caving and underground subsidence can be considered as the failure of a highly compacted rock and its subsequent flow in the form of broken rock. The problem is complex because the propagation of failure and flow have to be considered simultaneously; the yield strength of the virgin rock and the broken rock are different; and, while under certain conditions it is sufficient to consider the virgin rock as homogeneous, the density and the yield function of broken rock are both pressure and time dependent. A study of the failure and flow of solids with a pressure dependent yield function has been published recently by Jenike.' In this paper the density of the broken rock is assumed to be only time dependent and the consequences are examined in the case of one-dimensional vertical subsidence into an initial cavity. The following describes an attempt to develop a tool which, in combination with other tools, may lead to mathematical solutions of real problems of caving and subsidence. STATEMENT OF THE PROBLEM An underground cavity of horizontal cross section 4 = 1 and height 6 is assumed to exist at some depth below the surface. At the time t = 0 rock above the cavity fails and completely fills out the cavity with expanded broken material. With passing time the broken rock consolidates and subsidence proceeds continuously upuard in a vertical shaft. The phenomenon is one-dimensional (see Fig. 1). The problem consists of finding the displacement and the velocity with which the frlmt of the subsidence (wave front) moves upward as a function of the time and of the rock properties. DIFFERENTIAL EQUATIONS CONTROLLING THE PHENOMENON With the assumptions that the broken rock is a continuum and that the subsidence occurs continuously, we can apply the one-dimensional differential equation of contitiuity (conservation of mass) and the equation of preservation of momentum The latter equation is replaced by an assumed relation based on experience, which takes care of the

Jan 1, 1962

By Richard H. Hopkins, R. W. Kraft

A new technique facilitating the rapid determination of the three-dimensional morphology of phases suspended in an opaque matrix is described. The vapidity of the technique is based upon continuous cinephotomicrographic recording of specimen microstructure as the specimen surface is removed under controlled conditions in an electrolytic cell. The advantages of the technique for determining spatial morphologies in opaque materials are illustrated by application of this method to the study of the configuration of faults in a specimen of directionally solidified CuAl2-Al eutectic alloy. A spatial model of the eutectic fault network deduced in this manner has substantiated the facts that faults in this alloy tend to lie parallel to one another in a direction close to that of the specimen growth axis and that the majority of faults tend to bridge lamellae rather than run parallel to them as growth proceeds. For the specimen studied fault density decreased as growth proceeded. ALTHOUGH metallographic observation is a powerful tool for investigating the correlation between structure and properties in metallic alloys, ordinary metallographic methods suffer the fundamental limitation that any conclusions concerning the three-dimensional structure of these opaque materials must rely upon inference from two-dimensional microsections. For this reason it is frequently impossible to make valid judgments regarding the true spatial distribution of the micro-constituents in specimens under investigation. Several techniques have been devised to circumvent the basic limitation of planar microsec-tioning and employed with varying success. These include construction of three-dimensional models of alloy microstructure from sequences of photomicrographs,1-3 quantitative deduction of spatial features based upon statistical studies of data from random and/or selected plane microsections,4-6 and selective dissolution of one phase in a two-phase alloy to reveal the topography of the phase remaining.' However these techniques also have certain obvious disadvantages. Construction of three-dimensional models is a very time-con- suming procedure due to the tedious polish-etch-photograph cycle needed to obtain the necessary photomicrographs to portray the spatial microstructure. Statistical methods by their very nature give only average values of the quantities being studied and cannot therefore give a detailed physical picture of the microstructure to be observed. Finally, the technique of selective dissolution is only applicable in systems where the phases are of vastly different chemical reactivity; it is of little use in the study of single-phase alloys. Since the determination of the three-dimensional structure of opaque materials is hindered by two facts—the materials are opaque to radiation in the visible spectrum and construction of spatial models of microstructure is quite laborious—two solutions to the problem suggest themselves: 1) use radiation of energy great enough to render the alloy transparent, i.e., some microradio-graphic method, or, 2) devise a rapid means to section and record alloy microstructure. Stereomicroradiography has indeed been used to study internal arrangements of phases in several materials8,9 but the method, in general, is limited to very thin specimens (due to X-ray absorption) and simple microstructures. It would seem then that development of a rapid, simple, and generally applicable technique for studying the details of alloy microstructures in three dimensions can best be undertaken by following the second approach above. Using this idea a new technique for rapid evaluation of spatial microstructures was developed based upon cinephotomicrographic recording of the micro-structure of a specimen undergoing controlled electrolytic dissolution. It was further felt that application of this technique to the careful study of the spatial configuration of faults in a CuAl2-Al eutectic alloy would yield information that could be correlated with the extensive data3,6,10-12 already compiled concerning the solidification and crystallography of this eutectic. The practicality and usefulness of similar methods for studying three-dimensional features in alloys has recently been illustrated by the study of dislocation loops in zinc13 and spheroidized structure in steel.14

Jan 1, 1965

By G. H. Ruggles

POPULAR opinion, as it might be termed, has always been of the trend that a flotation reagent added to the ball mill during grinding would be more thoroughly mixed with the pulp and for that reason more effective in the production of low tailing. That there are other effects, inimical to good flotation, when using so-called chemical reagents, is brought out by the series of tests outlined in Table 2. It was defi-nitely proved that if either the T. T. mixture (20 per cent thiocarbanalid-80 per cent orthotoluidin) or po-tassium xanthate were added to the ball mill the result-ing flotation concentrate would be lower in copper and higher in insoluble than the concentrate produced by adding these same reagents without the ball mill cir-cuit. With the T. T. mixture four sets of tests were made. The screen analyses of the flotation feed show that there was very little difference in the original grind-ing. When the T. T. mixture was added to the head of the flotation machine the flotation concentrate had a little over 61 per cent solids -200 mesh. If the mix-ture was put into the ball mill the flotation concentrate had but 40.7 per cent of the solids -200 mesh for one set of tests, and 49.0 per cent for the other set. With the mixture at the head of flotation the total concen-trate was high in copper (34.715 and 36.525 per cent) and low in insoluble (13.20 and 11.61 per cent). The assay of the concentrate when the T. T. mixture was introduced into the ball mill was what might be termed low in copper (29.389 and 30.833 per cent). In one of these 'sets of tests (periods 8 to 11, third column) the insoluble was high, 16.81 per cent. The other run (peri-ods 12 to 15, fourth column) for some unknown reason shows a low insoluble, 12.72 per cent. With similar grinding the addition of potassium xan-thate to flotation produced a concentrate having 62.8 per cent -200 mesh, whereas with the potassium xanthate added to the ball mill the flotation concentrate was very coarse, only 36.4 per cent passing 200 mesh. The difference in the total assay of the concentrate is remarkable ; 35.847 per cent copper when the xanthate went to flotation and 30.44 per cent copper when the xanthate was added to the ball mill; insoluble, 10.94 per cent in the former instance, as 22.15 per cent in the latter.

Jan 8, 1927

By Barton, Donald C.

THE elastic, earthwaves produced naturally by earthquakes -have been used for a long time as evidence from' which to draw conclusions in regard to the constitution of the interior and crust of the earth. The elastic earthwaves produced artificially by occasional explosions and recorded by seismological .observatories were used to draw conclusions regarding the-geology of the intervening area. Intentionally produced elastic earthwaves in the past five years have come to be used extensively in the investigation of very local geologic structure. The seismic method of working geologic structure, which makes use of artificially controlled explosions and the resulting earthwaves, has developed almost `clairvoyant power in handling certain geologic situations, and in the discovery of salt domes in the Gulf Coastal: Plain region of Texas and Louisiana has 'scored the, most brilliant success.

Sep 1, 1928

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Can-anea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geologic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline. The headwaters of three rivers flowing to the Gulf of California are located in the Cananea Mountains: the San Pedro River, flowing to the north; the Sonora River, flowing south and west; and the Mag-dalena River, flowing west. Elenita Mountain, the highest point in the district, has an elevation of 8140 ft. The Cananea Mountains extend in a series of north-south to northwest-southeast spurs and ridges and are surrounded by gently sloping gravel plains. The mineralized area, lying across the southern and central parts of the range, is about 6 miles long and at most 2 miles wide. Elevations at the mines vary from 5300 ft at Cananea-Duluth mine at the southeast end of the district to between 6000 and 7000 ft at the west end of the mineralized area at Puertecitos-Elenita mines. Principal production has been from the intensely mineralized and altered area of Capote Basin in the central part of the district and the immediately surrounding area to the southeast. The district has produced over 2 billion lb of copper, substantial molybdenum, and minor amounts of lead, zinc, silver, and gold. Total production through 1949 is estimated at more than $300 million. In 1900 large-scale development was started at Cananea by W. C. Greene. Until World War II only high-grade ores were exploited; low-grade ores were extracted after the installation of a large concentrator in the early 1940's, and subsequent operations have been based upon mining and processing ores containing less than 1.0 pct copper from open-pit and underground workings. Mining and concentration of such low-grade ores, however, are made possible only by continued high copper prices, and active exploration for high-grade orebodies has been continued throughout the important mineralized areas. General Geology Study of the involved rock pattern at Cananea has indicated a complex geologic history for the district. Widespread alteration and mineralization have masked many of the salient features and have led to widely varying geologic interpretations over the years. Further work will probably disclose new information which will modify current beliefs. At Cananea a conformable series of sediments of probable Paleozoic age was deposited on an unknown basement. Following Paleozoic time there was an extended period of erosion common to many districts in the southwestern U. S., and there is no present evidence of marine sedimentation at Cananea after the Paleozoic. The eroded surface was eventually covered with a great thickness of extrusive volcanic rocks. The entire series of sediments and volcanic rocks was later intruded by a variety of deep-seated igneous rocks. These included the Cananea granite, the Cuitaca granodiorite, the El Torre syenite, the Tinaja diorite, the Campana diabase and gabbro and the Colorada rhyolite quartz porphyry. Faulting of early age, probably prior to the deposition of the volcanic rocks, may have been responsible for the present position of some of the intrusive rock masses. In the Capote mine on the third and fourth levels the northwest-striking Rick-etts fault zone, with apparent offset of about 800 ft, has been sealed by a dike-like mass of Cananea granite which gradually increases in size with depth. In lower levels of the mine the granite forms a large southeast-plunging mass generally following the course of the Ricketts zone. The granite is not known southeast of the Capote-Oversight mine areas and the Ricketts fault does not appear in the vol-canic~ southeast of Capote Basin, but several plugs of Colorada quartz porphyry cut the volcanics along the assumed general southeast trend of the Ricketts zone. These porphyritic intrusives may be the up-

Jan 1, 1955

Apr. 26-May 11, Liege International Fair, Liege, Belgium. May 4-8, Electrochemical Society, Inc., Spring meeting, Benjamin Franklin Hotel, Philadelphia. May 5-6, National Air Pollution Symposium, Huntington Hotel, Pasadena. May 5-7, American. Mining Congress, coal convention, Netherland Plaza Hotel, Cincinnati. May 6-9, Scientific Apparatus Makers Assn., annual meeting, Edgewater Beach Hotel, Chicago. May 9-10, AIME, joint meeting, Industrial Minerals Div. and Metals Branch, Davenport Hotel, Spokane, Wash. May 11-14, American Institute of Chemical Engineers, Atlanta Biltmore Hotel, Atlanta. May 17, AIME, Chicago Section, President's night dinner dance, Shoreland Hotel, Chicago. May 27, AIME, Morenci Subsection, Longfellow Inn, Morenci, Ariz. June 2-4, Chemical Institute of Canada, annual conference, Montreal. June 4-14, Mechanical Handling Exhibition and Convention, Olympia, London.

Jan 1, 1952

Jan 7, 1976

By D. B. RUSHNORE, K. A. Pauly

Bulletin. No. 41, May, 1910. ABBREVIATIONS. Al. Ind., Alliance Industrielle. am. Elec'n.. . American. Electrician. Bull. As. Ing. El Bulletin de la Association des Ingenieurs Elec- triciens Sortis de l'Institut Electrotecnique Montefiore, Liege. Bull. Soc. bilge d' Elec Bulletin de la Société belge d'Electriciens. Col. Guard . Colliery Guardian. D. R. P Deutsches Reich Patent. Dilly. Poly Dingler's Polytechniches Journal. E. & DI. Jour Engineering and Mining Journal. E. T. Zeit Electrotechnische Zeitschrift. Eclair. Elec. L'Eclairage Electrique. 1;1. Anzeig Elektrotechnischer Anzeiger

Sep 1, 1910

By C. T. Eddy, R. W. Drier

The conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in properry. or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest. Effect of Direction of Drawing In 1928 some work was done on hard-drawn copper wires to determine whether wire drawn in a continuous machine (that is, all in one direction) would have a different structure from wire that had a reversal in direction at some stage of the drawing process. The diffraction spectra obtained indicated that as the position of the wire rayed approached the core, a preferential crystal orientation existed, and that the closer to the core the more preferred was the orientation. The data obtained partly corroborated the work done by Schmidt and Wassermanl and by Clark.2 Samples Used in Following Investigation The samples selected for use in both the diffraction work and the resistivity measurements were taken from Nos. 6, 8, 10 and 12 gage

Jan 1, 1930

By D. G. Brubaker

IN the history of geophysical exploration by the electromagnetic method many procedures and types of equipment have been used. Source arrangements for surveying on the ground have included long wires grounded at both ends, large loops laid on the ground, small horizontal loops, and vertical loops of moderate to small sizes. Receivers have ranged from simple direction-finding coils to combinations of coils and a bridge circuit to measure quantities related to both amplitude and phase of the received signal. Primary considerations in choosing a survey method are effectiveness, speed, and economy. In work on the ground in which locating and out- lining conducting bodies is the objective, methods using a vertical coil and a simple direction-finder have been found the most satisfactory. Mason1 and his associates applied such a method by setting up a vertical source loop, fed with low frequency alternating current by an engine-generator set. With a direction-finding receiver they surveyed lines along the ground in the plane of the loop, taking measurements at each station of the azimuth and inclination of the magnetic field direction. Deviations of this direction from the normal direction, that is, from horizontal and perpendicular to the traverse line, indicated a conducting body. Recent advances in design of light-weight generating equipment have encouraged using this and similar methods.

Jan 7, 1957

By W. Vickers

SALKOVITZ1 has given a number of useful angles between planes for use with the Laue method in determining the orientation of bismuth single crystals. Bismuth is usually considered as having a face-centered-rhombohedra1 structure with its axial angle 87°34', Fig. 1. A similar figure given by Sal-kovitz appears to be in error in that the angle there marked as 87°34' should be 92°26. The primitive cell is a single rhombohedron of axial angle 570 14. The structure is almost face-centered-cubic and hence high accuracy in measurements is essential if there is to be no confusion in indexing poles or zone axes. It is easier to get this accuracy if zone axes are plotted on the stereogram because they will lie near the basic circle where the net has a more open scale. The zone axes can be read from the film, using a Greninger chart, and can be plotted more accurately than poles. Also, the angles between points near the basic circle can be read more accurately than those between poles near the center. In order to use the zone axes the angles between directions have been calculated from a formula given by Niggli,2 and are given in Table I. Miller indices

Jan 1, 1958

By R. Gatewood

The solution here offered is at once simple and important in its direct and indirect bearings. According to the principles of surface-tension, which will be found sufficiently enlarged upon for present purposes in Clerk Maxwell's excellent little treatise on The Theory of Heat, a mechanical mixture of liquids will frequently of itself divide into groups, consisting of liquids mixing among themselves but withdrawing from the other liquids. The following simple and familiar illustration will suffice: " If we mix water with alcohol, the liquids diffuse into each other. If we now attempt to mix oil with the alcohol and water, the two liquids separate from each other of themselves, and in the act of separation sufficient force is brought into play to set in motion considerable masses of the fluids." Maxwell goes on to show that this relative energy is one of arrangement, depending on the nature of the fluids and the area of the surface of contact, the act of separation tending to reduce this surface to a minimum consistent with equilibrium; that this surface-tension exists between a solid and touching fluid, either liquid or gaseous, being of one sign or the other, in the case of a liquid, according as it tends to draw itself up into a drop on its surface or to spread and wet the solid. After considering various cases, lie states that which particularly interests us, thus : " When a solid body is in contact with two fluids, then, if the

Jan 1, 1885

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By E. A. Anderson

In 1918 the American Society for Testing Materials held a symposium2 on what was then known as season cracking. The sessions included six papers, all on brass. During the ensuing 26 yr., many new workers have come into the field and several other metals have been found subject to failure by stress-corrosion cracking when the right combination of stress and environment is achieved. It is not surprising, therefore, that the present symposium has brought forth 29 papers covering alloys of seven important metals. The phenomenon of stress-corrosion cracking is not necessarily confined to these seven metals. Dix3 has stated, "Indeed, it is probable that ingenious investigators can find solutions which will stress-corrosion crack any known metal or alloy." Mears, Brown, and Dix4 have indicated that stress- corrosion cracking failures are not necessarily limited to metals but may include the plastics. It is to be expected that the increase in the number of metals known to crack in service and the general emphasis on such failures at a symposium such as this will alarm many to whom the subject is un- familiar. Such alarm is not justified by the record. It is true that stress-corrosion

Jan 1, 1945

By Jesse O. Betterton, Y. E. Lebedeff

AS a matter of the most widespread interest to lead-refining metallurgists, the process of desilverizing lead originated by Parkes is the most fundamental step in lead refining. While this basic operation, in addition to effecting a practically complete recovery of gold and silver, is also a great purifying operation and a governor on the purity and uniformity of the final refined lead, it has the important deficiency that no bismuth is removed in the operation. The problem of finding a satisfactory, inexpensive method for removal of bismuth that would fit in with the basic desilverization step has been one of enticing interest for lead-refinery metallurgists for many years. Of late it has become one of imperative interest, and while many attempts and much progress have been made, it is probably fair to say that metallurgical progress thus far is only catching up with commercial requirements. The Pattinson process, an original competitor of the Parkes process for desilverization, has received much attention for its possibilities for bismuth removal. Bismuth concentrations in the Pattinson process fall far short of the silver concentrations and as a result too many operations are required and a crawl in grade in the kettle units is experienced which requires periodic correction. Altogether, it has proved too expensive a remedy, from the cost standpoint of both installation and operation. The Betts electrolytic process is a fully satisfactory remedy but its present status in the field of lead refining is more a matter of bismuth removal than preference as a refining system, except, of course, in instances particularly favorable to the basic requirements of the process. The Betts process, of course, is essentially different from the Parkes process, and very difficult to associate therewith to any economy except in minor ways. Accordingly, where economy dictates the Parkes process, and this is true of far the greater portion of the world's tonnage, the adoption of the Betts process primarily for bismuth removal is apt to prove an expensive remedy on account of its normally higher cost of operation, inelasticity of the equipment for variable tonnages, and high per ton cost of installation.

Jan 1, 1937

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh' Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949

By C. D. Woodward

ThE subject of elcctric signals for the despatching of mining cagey through shafts has received cousiderable attention recently from various mining companies. The Anaconda Copper Mining Co. has found it necessary to develop a system that is rcliable, safe and simple in operation, and easy to repair. The movement of all mine cages or skips is under the direction of a station tender, who rides on the cages when men or supplies are being lowered or raised; when ore is hoisted, he is stationed at a skip pocket for loading and despatching the skips. For the station tender's use, two signal systems are installed in cach hoisting compartment, and he is the only employee authorized to use them. One system is known as the "AC " or station bells, as it is operated from the 110-volt, 60-cycle, power service; the other system, called the "DC" or shaft bells, takes its energy from closed-circuit primary batteries. As a supplemcnt to the two main signals, a buzzer system is installed The general arrangement is similar to the main signal, except that there is a mine buzzer at each station. When a signal switch connected into the buzzer system is pulled down, all buzzers arc operated, thus notifying the station tender that he is wanted at seine particular level. Placed on the station posts, and within easy reach of the men on the cages are the signal pull switches for the main signals. The station, or "AC," pull switches are furnished with a short rope as shown in Fig. I, while the shaft, or "DC," pull switches are equipped with ropes that extend down the shaft past the next station. To avoid all confusion in the use of the three signal systems, a standard arrangement has been adopted in all mines for the location of the pull switches. Fig 2 illustrates the position of the pull switch at the various mine stations for the main signal systems, but it does not show the buzzer pull switch; this is fixed to the roof timbers about 25 ft. back from the shaft. If the skip pockets are a considerable distance below the station, a pull switch for each main shaft compartment is connected to the "AC" system and placed at this point. However, if the distance is short, a light cord is attached to the station pull switches and dropped down to the skip pocket.

Jan 1, 1923

By C. D. Woodward

ThE subject of elcctric signals for the despatching of mining cagey through shafts has received cousiderable attention recently from various mining companies. The Anaconda Copper Mining Co. has found it necessary to develop a system that is rcliable, safe and simple in operation, and easy to repair. The movement of all mine cages or skips is under the direction of a station tender, who rides on the cages when men or supplies are being lowered or raised; when ore is hoisted, he is stationed at a skip pocket for loading and despatching the skips. For the station tender's use, two signal systems are installed in cach hoisting compartment, and he is the only employee authorized to use them. One system is known as the "AC " or station bells, as it is operated from the 110-volt, 60-cycle, power service; the other system, called the "DC" or shaft bells, takes its energy from closed-circuit primary batteries. As a supplemcnt to the two main signals, a buzzer system is installed The general arrangement is similar to the main signal, except that there is a mine buzzer at each station. When a signal switch connected into the buzzer system is pulled down, all buzzers arc operated, thus notifying the station tender that he is wanted at seine particular level. Placed on the station posts, and within easy reach of the men on the cages are the signal pull switches for the main signals. The station, or "AC," pull switches are furnished with a short rope as shown in Fig. I, while the shaft, or "DC," pull switches are equipped with ropes that extend down the shaft past the next station. To avoid all confusion in the use of the three signal systems, a standard arrangement has been adopted in all mines for the location of the pull switches. Fig 2 illustrates the position of the pull switch at the various mine stations for the main signal systems, but it does not show the buzzer pull switch; this is fixed to the roof timbers about 25 ft. back from the shaft. If the skip pockets are a considerable distance below the station, a pull switch for each main shaft compartment is connected to the "AC" system and placed at this point. However, if the distance is short, a light cord is attached to the station pull switches and dropped down to the skip pocket.

Jan 1, 1923

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.' investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.' EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969