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By A. H. Daane, J. F. Haefling

BECAUSE of the wide use of platinum in industry and research, the physical properties of this metal, including its vapor pressure, have been studied in some detail.' The other members of the palladium-platinum group of metals have not been studied as extensively, and only qualitative information is available on the vapor pressure of palladium. Data given in literature by Vines1 and Brewer2 on the vapor pressure of palladium are based on the qualitative observations by Holborn and Austin3 and Crookes4 on the rate of volatilization of palladium filaments in various atmospheres. The general observation that palladium is the most volatile metal of the palladium-platinum metal group was corroborated by Bell, Love and Normand who studied the separation of isotopes of the platinum-group metals by a mass spectrometric method. We have measured the vapor pressure of palladium using the Knudsen effusion technique. In this work, the effusion vessel was suspended from a quartz-fiber microbalance into an induction furnace, and the amount of vapor effusing from the vessel was determined by direct weighing of the vessel during the measured heating times. This technique has been described in a report from this laboratory." The vapor pressure of palladium was calculated from these measurements using the equation P...... = 17.14 -W- (77m)'u [1] a t where ? is the weight loss in grams of vapor of molecular weight m from a vessel having an orifice of a sq cm, during t sec. The derivation of this equation from kinetic theory has been described in a previous report from this laboratory: as well as in texts discussing the kinetic theory of gases.%" Test Vessel—In the search for a suitable material for the effusion vessel, it was found that tantalum reacted with palladium metal to form intermetallic compounds, and graphite was readily dissolved in palladium metal to form what appeared to be a liquid phase at a temperature several hundred degrees below the melting point of palladium. On cooling, the graphite gathered into spherical balls in the palladium, with crystals extending radially from the center of these balls, some of which were a millimeter or more in diameter. However, palladium metal vapor did not attack the graphite vessel, so graphite could be used where it did not contact condensed palladium. Tungsten did not appear to react with palladium vapor or molten palladium at its melting point, but it was not convenient to use a tungsten-vapor pressure vessel because of the difficulty of fabricating this metal. Since the vapor-pressure range to be studied (10 2 to 10 ' mm) did not appear to extend above the melting point of palladium, a combination of tungsten and graphite served to provide a very satisfactory effusion vessel. The lower half of the graphite vessel was lined with some strips of tungsten foil and the sample of palladium consisting of a coil of sheet was placed in the tungsten liner; in this way, no contamination of the palladium by carbon occurred. Procedure After outgassing at 1500C, the tungsten-lined graphite effusion vessel was loaded with 300 mg of

Jan 1, 1959

By Cyril S. Taylor, Junius D. Edwards

Magnesium is the lightest metal used for structural purposes, for which reason perhaps more than usual interest is attached to measurements of its density. Although the density of solid magnesium has been det,ermined frequently, no measurements of the density of the liquid metal are available. Because of unusual experimental difficulties in measuring the density of the liquid, only a limited number of measurements of good precision were secured. The results, especially the value for the crystallization shrinkage, are of great interest in connection with the casting of the metal. A number of samples for these measurements were made available through the courtesy of the American Magnesium Corp. They were in the form of extruded bars 3/8 in- in diameter and several were of exceptional purity, as indicated by careful analyses. Table 1 gives the density values (at 20" C.) for magnesium of varying degrees of purity. The density was measured at room temperature by comparison of the weight in air, and when immersed in distilled water. The necessary buoyancy corrections were applied, so that the density could be expressed in absolute measure—grams per milliliter. The effect of the buoyancy of the immersed suspension and the surface-tension pull of the water upon the suspension were eliminated from the results by a preliminary weighing of the suspension immersed to the working depth. Great care was necessary to prevent the introduction of a significant error by the formation of gas bubbles upon the clean magnesium surfaces; these are sometimes very minute and easily escape observation. They may be detached by raising the specimen from the water and again immersing; this should be done just prior to completing the weighing. Their formation may be almost entirely prevented during a measurement by previously immersing the specimen in a solution of paraffin in petroleum ether. The thin film of paraffin remaining after the evaporation of the solvent prevents wetting of the magnesium surface by the water. In one such determination, the paraffin coating on a 22-gm. Specimen

Jan 1, 1923

By Junius D. Edwards, Cyril S. Taylor

Magnesium is the lightest metal used for structural purposes, for which reason perhaps more than usual interest is attached to measurements of its density. Although the density of solid magnesium has been det,ermined frequently, no measurements of the density of the liquid metal are available. Because of unusual experimental difficulties in measuring the density of the liquid, only a limited number of measurements of good precision were secured. The results, especially the value for the crystallization shrinkage, are of great interest in connection with the casting of the metal. A number of samples for these measurements were made available through the courtesy of the American Magnesium Corp. They were in the form of extruded bars 3/8 in- in diameter and several were of exceptional purity, as indicated by careful analyses. Table 1 gives the density values (at 20" C.) for magnesium of varying degrees of purity. The density was measured at room temperature by comparison of the weight in air, and when immersed in distilled water. The necessary buoyancy corrections were applied, so that the density could be expressed in absolute measure—grams per milliliter. The effect of the buoyancy of the immersed suspension and the surface-tension pull of the water upon the suspension were eliminated from the results by a preliminary weighing of the suspension immersed to the working depth. Great care was necessary to prevent the introduction of a significant error by the formation of gas bubbles upon the clean magnesium surfaces; these are sometimes very minute and easily escape observation. They may be detached by raising the specimen from the water and again immersing; this should be done just prior to completing the weighing. Their formation may be almost entirely prevented during a measurement by previously immersing the specimen in a solution of paraffin in petroleum ether. The thin film of paraffin remaining after the evaporation of the solvent prevents wetting of the magnesium surface by the water. In one such determination, the paraffin coating on a 22-gm. Specimen

Jan 1, 1923

THE first session, on alloys, took place on Feb. 20, Mr. Hibbard presiding in Mr. Campbell's absence. The session covered papers on manganese, chrom-ium, and silicon-iron systems. The paper by Mr. Wohr-man was presented by title. This paper showed that manganese produced many of the effects generally at-tributed to carbon and indicated that our ideas on manganese-bearing carbon steels will have to be modi-fied. Mr. Krivobok discussed this paper at length, the gist of the discussion being that Mr. Wohrman had not taken sufficient precautions in carrying out some of his work, particularly as to the effect of silicon content. Mr. O'Neill's paper was also submitted by title and no discussion was presented. Mr. Kinzel showed an accu-rate determination of .the carbon-free chromium-iron loop obtained by means of a specially constructed tele-scopic dilatometer. The loop ends at 12.2 per cent chromium and the A-3 line at 900° is unaffected by chromium content. The A-4 line runs from 1400° to 900° at 12.2 per cent chromium as an oblique hyperbola. Mr. Armstrong noted that the brittleness in high chromium alloys is often attributed to the gamma trans-formation and, according to Mr. Kinzel's diagram, this was impossible, as the alloys contain a great deal more than 12 per cent chromium. Mr. Kinzel pointed out that the presence of carbon in the commercial alloys caused the elongation of the loop and made possible local austenite transformation. Mr. Styri discussed the relations of the coefficients of expansion as shown in Mr. Kinzel's diagram. Mr. Corson presented the iron-silicon diagram as he has worked it out, showing a pre-viously unknown intermetallic compound, Fe3Si, to-gether with characteristic martensitic microstructure varying with the heat treatment. This compound formation is the real cause of brittleness in certain re-gions of the iron silicon system. Dr. Hoyt believed some of the evidence presented by Mr. Corson to be in contradiction to the phase rule. Mr. Corson, however, explained that true equilibrium does not exist under the conditions at hand so that the diagram was accurate in spite of the discrepancies. The meetings of the subcommittee on the physical chemistry of steel making were interspersed through-out the day. Mr. Feild presided and a program of future activities was outlined. This includes plans for a symposium at the next annual meeting and methods for interesting physical chemists, particularly those in the universities, in the steel man's problems. This committee has been newly formed and bids fair to be especially active. The Iron and Steel Committee met at lunch at the Engineers' Club at noon, with Dr. Mathews presiding. After disposing of the food the report of the Nominat-ing Committee was called for, and the following were elected as officers for 1928: R. H. Sweetser, chairman; F. C. Langenberg and W. J. Priestley, vice-chairmen; and T. T. Read, secretary. The report of the commit-tee appointed at the last meeting to consider publica-tion and general policy for the committee was then called for and freely discussed, after which it was unanimously voted to instruct the new chairman to se-cure from the Board of Directors the necessary author-ization for the Committee to recognize as a Division. This action was reported to the Board at its meeting the following night and the authority granted.

Jan 3, 1928

By C. G. Albert

The literature of paper technology contains a number of articles having reference to developments in the field of coating and filler clays for use in paper manufacture. Much of this information has not been included in mining publications and has therefore not been readily available to all in the mineral industry. Recent developments in this field, including spray drying of clays, are presented here. U. S. Bureau of Mines figures for 1952 indicate that the paper industry consumes more than 50 pct of all kaolin produced and sold in the U. S. As most of the kaolin used by the industry comes from Georgia producers, the fraction of their output destined for paper use is thus appreciably higher than 50 pct. Small wonder that the kaolin industry, especially in Georgia, is highly sensitive to the quality requirements of paper mills and must respond promptly to technological developments in paper manufacturing.

Oct 1, 1955

By Wilhelm Flesch

THE object of development work in the field of gasification is to find a process by which all' fuels, regardless of their individual properties, can be gasified economically. This paper describes the development of the Winkler process. The economy of the gasification process depends not only on the degree of the gasification effect but also, to a decisive extent, on the costs of fuel, production, and installations. Fig 1 shows the relation between fuel costs and gasification efficiency for various types of fuels. Since the fuel cost in the gasification of coke amounts to two thirds of the price of gas, and the thermal unit in brown coal costs only one third of what it costs in coke, it is easily seen how profitably cheap fuels can be gasified, especially if these fuels require minimum preparation and gasification is done in the vicinity of the mines. These possibilities were a great advantage of the Winkler generators, which were installed 20 years ago in the central German brown-coal fields and, at that time, were without rival for the gasification of finely divided fuels. In the Winkler generator (Fig 2), crushed and ground solid fuels were, for the first time, successfully gasified with oxygen and steam on an industrial scale. Unlike the usual processes formerly employed on an industrial scale, this gasification, which proceeds continuously in the glowing, seething fuel bed, makes only extremely low demands on the fuel. The fuel no longer has to be in lumps and abrasion-resistant, but must be capable of reaction and must be fed into the generator in a grain size of 0 to 8 mm. Brown coal or bituminous coal, or their low-temperature cokes, can be gasified in the Winkler generator. Large plants using fuels are operating on an industrial scale in Europe and in Japan. Table 1 shows the results obtained by gasifying these, fuels in Winkler generators. The thermal efficiency of gasification, which is the relation between the calorific value obtained in the gas produced and that of the fuel consumed, gives no indication of the quantity of steam generated in gasification. The generation of steam in the waste-heat boiler of the Winkler generator adequately-covers the steam consumed in gasification. To obtain effective gasification in the Winkler process, combustible mate-

Jan 1, 1953

By John D. Sullivan, Chester R. Austin, Edwin J. Rogers

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By Wilbur I. Duvall, Wilson Blake

The microseismic method of detecting instability in underground mines was developed by the U.S. Bureau of Mines (USBM) in the early 1940's. ,3 The method relies on the fact that as rock is stressed, strain energy is stored in the rock. Accompanying the buildup of strain energy are small-scale displacement adjustments that release small amounts of seismic and acoustic energy. These small-scale disturbances, which can be detected with the aid of special geophysical equipment, are called micro-seisims or self-gene rated rock noises. It was further determined that as failure of rock is approached, the rate at which rock noises are generated increases. Thus, by monitoring a rock structure at intervals and plotting rock noise rates vs. time, a semi quantitative estimate of the behavior and stability of the structure can be made. Since sufficient use of the microseismic method is still being made by various mining and construction companies, USBM undertook a comprehensive review of the method and a study of the fundamental properties of rock noises. As all prior work on rock noises has been done with resonant-type geophones, which prevented any analysis of their vibration records, it was necessary to develop the instrumentation and field techniques in order that their properties could be investigated, such as their frequency spectrum and absorption characteristics, and to determine if both P and S-waves are generated by a rock noise. The aim of this program is the design of microseismic instrumentation which can be better utilized as an engineering tool than the presently available microseismic equipment. This new design, based on the basic properties of rock noises, should allow better utilization of these phenomena in the study and location of zones of incipient instability in both underground and open-pit mines. EXPERIMENTAL PROCEDURE To study the waveform of rock noises, it was necessary to develop a microseismic system with a broad bandwidth. To achieve high sensitivity and broad frequency response, commercial ceramic accelerometers were used. The present broad-band microseismic system consists of accelerometers as geophones, low-noise preamplifiers, high-gain amplifiers, and an FM magnetic tape recorder. This seven-channel system has a flat frequency response from 20 to 10,000 Hz, a noise level of less than 2.0 kv, and a dynamic range (including manual set attenuation) of greater than 100 db; it can detect signals with acceleration levels as low as 2 ug. The entire system is solid state and hence battery operated and portable (Fig. 1) Analysis procedures consist of playing back the 30-in-per-sec (ips) magnetic tape recordings at 1 7/8 ips to expand the time scale of a recorded rock noise event and then recording this on a high-speed direct-writing oscillograph. The oscilIographic records are then digitized and run through Fourier integral analysis computer programs to determine the frequency spectrum of a rock noise event. The oscillographic records are also examined visually to determine if both P and S-waves can be recognized in a rock noise waveform. Broad-band microseismic recordings have been made at field sites in a wide variety of rock types and in both underground and open-pit mines. Sites include the Kimbley Pit, Ruth, Nev.; the Galena Mine, Wallace, Idaho; the Colony Development Mine. Grand Valley, Colo.; the Cliff Shaft Mine, Ishpeming, Mich; and the White Pine Mine, White Pine, Mich. DATA AND DISCUSSION Analyses of the recorded data have shown that rock noise frequencies are very broad. Fig. 2 and 3 show typical rock noise events and their frequency spectrums. In addition, it is evident from these figures that the wave form of a rock noise is very complex. The wide frequency variation, 50 to 7500 Hz, is due to many variables; the effect of travel distance is the only one examined in this study. The higher frequency components of the wave are rapidly absorbed with distance or increasing travel time. Fig. 4 shows the change in waveform resulting from an additional travel distance of 195 ft. From these data, it is apparent that a resonant-type microseismic geophone cannot respond to all frequencies generated by a rock noise, and in spite of the fact that the tuned geophone is more sensitive at resonance, a geophone with less sensitivity but broader band width is much more effective in detecting rock noises. In addition, a study of broad-band microseismic records shows that both P and S-wave arrivals are easily detected, as shown in Fig. 5. All records analyzed to date show that most of the energy is in the S portion of the wave; hence, microseismic geophones should be well

Jan 1, 1970

By Henry T. Mudd

FLUORSPAR is a nonmetallic mineral aggregate or mass containing a sufficient quantity of fluorite (CaF2) to be of commercial interest. It has only moderate value per unit of weight and its cost as a percentage of the cost of finished consumer products is nearly negligible. Nevertheless, it has wide and great industrial importance. In periods of national emergency it is a mineral without which many very necessary manufacturing processes would be greatly handicapped; a few could not exist. Fluorite contains 51.1 pct calcium and 48.9 pct fluorine. Industrial grades of fluorspar prepared for the consumer normally contain from 85 to 98 pct fluorite, depending on the use. The ores may contain as little as 30 pct fluorite, depending on many factors such as accessibility to transportation and markets, character of ore, and prices. Fluorite is a lustrous, glasslike mineral, generally translucent to transparent; it may be clear and colorless or range in color from slightly bluish through various shades of violet, amethyst, purple, green, and yellow. It crystallizes in the isometric system and possesses perfect octahedral cleavage. Commonly it occurs in masses of very pure crystal- line material with aggregates of cubical crystals in open spaces, but - it is also found in fine to coarse granular form. Banded veins and masses with fibrous, radiating structure occur locally. It is usually found associated more or less intimately with other minerals and rocks, from which it must be separated for commercial use. The specific gravity of fluorite is 3.18 and the hardness is 4 in the Mohs scale, compared with 7 for quartz and 3 for calcite. It is distinguished from calcite by its failure to effervesce with dilute hydrochloric acid. Heated with sulphuric acid, it gives off fumes of hydro- fluoric acid, which etch glass.22,25,33.34,35.41

Jan 1, 1949

By J. B. Clark, A. J. McEvily, R. L. Snyder

The nonuniform distribution of precipitate particles has been recognized as a leading factor contributing to the relatively low fatigue resistance of aluminum alloys. The structure of many of these alloys is characterized by narrow precipitate-free zones adjacent to the grain boundaries. Alloys with such zones exhibit a tendency for brittle inter crystalline fracture. The interrelation between this type of structure and mechanical properties was investigated in an Al-10 wt pct Mg alloy. It was found that deformation during fatigue occurs preferentially along these zones and cracks initiate there. In Al-10wt pct Mg, the zones were found to be supersaturated even after extensive general precipitation and are due to the absence of proper precipitate nuclei in the region near the grain boundaries. Cold working the alloy prior to aging improves the mechanical properties by inducing precipitation within the zones and also by jogging of grain boundaries. The mode of fracture is changed from brittle inter crystalline to more ductile trans granular fracture. THE process of fatigue is highly structure sensitive, with the strength of the whole often dependent upon some localized discontinuity, either geometrical or metallurgical in nature. Much has been learned about the role of geometrical discontinuities, e.g., notches, in fatigue, but with the exception of the effects of inclusions or the shapes of carbides, relatively little is known about the specific effects of discontinuities in metallurgical structure such as nonuniform precipitation. In most age-hardening aluminum alloys, metallo-graphic studies have shown that the extent of precipitation adjacent to grain boundaries is much less than that which occurs in the interior of the grains. The width of these almost precipitate-free regions, which are sometimes called denuded zones, and the extent of solute depletion within them, are dependent upon the particular alloy and its aging treatment. It has been observed1 that these zones are relatively soft with the result that plastic deformation takes place preferentially within them. It has also been shown 2-4 that there exists a tendency for intercrys- talline cracking in fatigue when such zones are present. It is of interest to note that Broom et al.2,3 were able to reduce the incidence of this type of failure in an A1-4 wt pct Cu alloy by stretching the material 10 pct prior to aging. In the present study, the effects of precipitate-free regions on the fatigue properties of an A1-10 wt pct Mg alloy were studied in detail, and the effects of deformation prior to aging on the nature of the precipitation process as well as on fatigue properties were also investigated. MATERIAL AND PROCESSING An A1-10 wt pct Mg alloy was selected for this study, because it was known that well-defined precipitate-free regions along the grain boundaries are readily obtained in this alloy after aging at 200oC.5 The starting materials were 99.998 pct A1 and singly sublimed magnesium of about 99.9 pct purity. The aluminum was induction melted in a graphite crucible, and then the magnesium addition was immersed until dissolved. Chlorine gas was then bubbled through the molten alloy for 4 min to degas the melt, after which the melt was cast at a pouring temperature of 730" to 760°C into a cold, graphite-coated, tapered steel mold. Since A1-Mg alloys are difficult to homogenize,5 special care was taken to obtain a uniform composition. Two-in. cubes were cut from the ingot and heated at 446°C for 30 min. These cubes were then hot forged approximately 35 pct in each of the three cube directions and homogenized for 16 hr at 446°C. Sheet specimens were then obtained by pressing 40 pct and rolling 35 pct per pass with reheating between reduction steps to a final thickness of approximately 0.10 in. The sheet was then solution treated for 16 hr at 446°C and water quenched. The age hardening behavior of this material at 200°C was then determined, and the results are shown in Fig. 1. The age hardening of this alloy when subjected to cold work prior to aging is also shown in this figure. Preliminary work indicated that extensive deformation after quenching was required to affect drastically the precipitate-free regions in this alloy, and a rolling reduction of 50 pct was chosen. For purposes of comparison the following three conditions were studied: a) Solution treated, quenched, and aged 20 hr at 200°C

Jan 1, 1963

By C. P. Karr

FOR several years, the Bureau of Standards has been working in cooperation with an Advisory Committee on non-ferrous metals on various phases of the production and testing of zinc bronzes. The work has dealt, especially with the type of metal known as "Admiralty bronze" in England and as "Government bronze" in this country and consisting of 88 copper, 10 tin, and 2 zinc. Several reports have been made on this subject and these should be considered in connection with this paper.1 FIRST SERIES OF FIVE FOUNDRY TESTS A very brief summary of the first series of five foundry tests has been made,2 but for the sake of clearness the results are given here in different form. The five foundries cooperating in this investigation were: Ohio Brass Co., Mansfield, Ohio; Titanium Alloy Mfg. Co., Niagara Falls, N. Y.; Packard Motor Car Co., Syracuse, N. Y.; National Cash Register Co., Dayton, Ohio; Bureau of Standards, Washington, D. C. The object of the work was to determine whether uniform results could be obtained with this alloy in different foundries working under definite instructions. One of the participating foundries prepared, from virgin metal, a stock of ingots of the composition 88 copper, 10 tin, 2 zinc, and at the same time poured nine test bars from this melt of virgin metal. The results of the physical tests of these bars are shown in Table 1. Examination of this table shows that the highest and most nearly uniform results were obtained when the virgin metal was cast flat in chill molds and the lowest and most variable results were encountered when it was cast vertical in green-sand molds. In this, as in all other tables, the mean

Jan 9, 1919

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation' dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,' and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.' A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By F. C. Sturges

By definition the word "grout" means a thin mortar, or a kind of plaster or cement, and "grouting" means to fill up or finish with grout. The words "cement," "plaster" and "mortar" mean a substance that is used in a soft state which subsequently hardens. Thus, grouting is the filling of void space with a substance that hardens. Construction cements are the most common substances used, either by themselves or in mixtures, but the term grouting is applied quite correctly when other substances such as plastics and certain chemicals are used. Also, the use of the term grouting to cover the filling of voids with materials that do not actually become hard, such as the flotation tailings used in grouting in the southeast Missouri lead district, should be considered correct, as some stiffening does take place and, anyway, it is a better descriptive term than any substitute. Engineers are interested in grouting because some of the materials with which they must work contain voids, and certain conditions can be improved if these voids can be filled with something solid and permanent. Grouting is done to accomplish several purposes: I. To stop the passage of fluids and gases, 2. To cement materials together to make them stronger, and 3. To prevent consolidation of materials by filling void space with something solid as a replacement for the air and water that could be forced out under load. The construction industry uses grouting extensively for all three purposes. Grouting is used to stop water percolation under and around dams. It is used to control water flow in tunnel driving and in shaft sinking. It is used to improve foundation conditions under civil engineering structures by permanently filling void space and thereby reducing settlement, or by cementing broken rock together and increasing its supporting strength. The oil and gas industry does a lot of grouting, primarily to stop the passage of gases and fluids. The search for oil at increasingly greater depths has meant greater investment per well, and the oil industry has spent large sums on development of improved drilling methods. This

Jan 1, 1949

By Cyril Stanley Smith

Although not of the same importance as electrical conductivity, the capacity for conducting heat is nevertheless a very important property of metals and alloys. A knowledge of thermal conductivity is of value in selecting alloys for many purposes and in the calculation of the efficiency of apparatus which is being designed. Unfortunately, the determination of thermal conductivity is extremely slow and tedious, consequently few data have been obtained. A further reason for the lack of information is that there has long been an impression that the thermal conductivity of an alloy is directly proportional to the electrical cónductivity and that it can therefore be calculated from the latter. The Wiedmann-Franz-Lorenz law of constant ratio of the two conductivities holds with a considerable degree of precision for all the pure metals, but appreciable deviations occur in certain alloys—particularly those containing nickel—and it seems difficult to predict exactly what the ratio will be. Therefore direct determinations of thermal conductivity should be made whenever the results are needed with any accuracy. This research is intended eventually to cover all the alloys of copper that are of commercial importance, including the binary alloys of copper with zinc, tin, aluminum, nickel, silicon, manganese, cadmium and phosphorus, and the ternary alloys copper-nickel-zinc, copper-nickel-silicon, copper-manganese-silicon, copper-zinc-tin, etc. Most of these alloys are customarily used in the wrought condition and therefore were tested in the form of annealed rods. A limited number of sand castings were also obtained and examined. This paper contains a complete review of all the previous work that has been done on copper alloys, and includes a detailed description of the apparatus and method of procedure used in the present research, together with the new results obtained on the copper-zinc series, which is the only one completed at the present time. Subsequent papers describing the other alloys will contain the experimental results and discussion only. Previous Work Copper The conductivity of copper has been studied by many observers since the pioneer work of Wiedemann in 1859. The majority of these measure-

Jan 1, 1930

BECAUSE of the impetus given to placer mining since the price of gold was advanced to $35, several types of small dredges have made their appearance, especially in the Lincoln and Oroville areas of California. Some of these are known as "doodle bugs," and have been given considerable publicity, though many believe their performance has been overrated and that complete costs of construction and operation, if known would not put them in so favorable a light. Fig. 1 is a doodle bug owned by E. M. Clark and operated near Lincoln, Calif. It is understood that it was abandoned because of inability to handle deep ground. A similar machine that has been operated-profitably by Comstock Placers is shown in Fig. 2.

Jan 1, 1938

By T. G. Digges, M. R. Achter

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By E. R. Buchanan, R. E. Reed-Hill

Cylindrical magnesium single crystals were deformed in torsion. The axis of torsion was the basal pole. Five crystals were deformed to different strains between 0.08 and 1.03 and then sectioned in order to determine their dislocation densities using the transmission electron microscope. The work hardening rate of all specimens was at least an order of magnitude higher than that normally associated with easy glide in a tension test and comparable to that obserzed in stage B of a tension test. The correspondence between stage B in a tension test and the initial stages of a torsion test is believed to result from the fact that in both cases deformation occurs in a structure containing roughly equivalent densities of the dislocations associated with the three basal slip vectors. THERE are three basic ways of changing the shape of a crystal using slip dislocations. The crystal can be sheared along a slip direction in a slip plane; it can be bent about an axis in the slip plane normal to the slip direction; and, if the slip plane contains multiple slip directions, it can be twisted or rotated about the slip plane normal. Of the three processes, generally known as translational, flexural, and rotational slip, only rotational slip has not been extensively investigated. The object of the present research was to obtain basic information about this phase of crystalline plasticity. This paper is concerned with some aspects of the stress-strain curves obtained by twisting magnesium crystals about their basal poles. Magnesium was selected for four reasons. One, its recovery rate at room temperature is relatively low. Two, single crystals may be easily grown. Three, at room temperature the critical resolved shear stress for basal slip is about two orders of magnitude lower than that for nonbasal slip, so that rotational slip might be expected to occur primarily by basal slip. Finally, relationships between flow stress, shear strain, and dislocation density have been determined for tensile deformation of magnesium crystals,' thereby providing a basis of comparison for the torsional results. EXPERIMENTAL PROCEDURES Crystals were grown from 0.5 in. diam extruded sublimed magnesium rod furnished by the Dow Chemical Co. who reported that it contained in weight percent less than 0.0003 Al, 0.01 Ca, 0.01 Cu, 0.0012 Fe, 0.001 Mn, 0.0005 Ni, 0.003 Pb, 0.001 Si, 0.01 Sn, and 0.02 Zn, with the balance magnesium. All crystals were grown in a dried argon atmosphere using Jill-son's2 modified Bridgman technique. Two different methods were used to obtain crystals with the basal plane normal to the specimen axis. These included direct growth from seeds of the proper orientation, and spark machining (trepanning) of 0.5 in. diam cylinders from larger (1.5 in. diam) randomly grown crystals. The crystals thus produced were polished in a 20 pct HC1 water solution and then etched in a 1 pct HC1 water solution to develop etch pits lying in rows parallel to the basal plane trace. The crystals were then revolved about their axes on the stage of a low-powered microscope. Torsion specimens were prepared only from those crystals whose axes were normal to the rows of etch pits. It is estimated that this simple orientation method was accurate to about 51 deg. 1.625 in. long cylinders were next cut from these selected crystals and then acid machined in a 20 pct HC1 water solution into torsion specimens with a 1 in. long by 0.30 in. diam reduced gage section. Following this, they were annealed in air at 400°C and furnace cooled to room temperature. The specimens were given a final polish in a 10 pct HC1 water solution, rinsed in ethanol, dried, and cemented into brass grips with an epoxy resin. In addition to the torsion specimens, several tensile specimens with their basal planes at 45 deg to the stress axis were also prepared with similar dimensions except that the gage sections were increased to 4 in. in length. The torsion specimens were tested in the apparatus

Jan 1, 1970