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By W. M. Albrecht, W. D. Klopp, R. I. Jaffee, B. G. Koehl

Kinetic studies were made of the reactions of tantalum with oxygen, nitrogen, and air at 400o to 1500°C. The tantalum-oxygen reaction is linear from 500° to 1250°C. The tantalum-nitrogen reaction follows a cubic rate law at 400° to 700°C and a parabolic rate law at 800" to 1475°C. The reaction behavior in air is initially parabolic followed by a transition to linear behavior. In the search for high-temperature materials, considerable interest is being shown in the refractory metal, tantalum. It is the third highest melting metal with a melting point of 2996°C. Also, tantalum has excellent ductility, making it one of the most workable refractory metals. In considering high-temperature applications of tantalum, the oxidation kinetics of the metal must be known. Such information also serves as a basis for the development of corrosion resistant tantalum-base alloys. Therefore, this study was made to investigate the reaction of tantalum with air, nitrogen, and oxygen. LITERATURE Several oxides of tantalum have been reported. The pentoxide, Taz05, is the only oxide of tantalum whose identity has been established. A high-temperature modification, aTa2Os, has been reported by several investigators.1-4 A low-temperature phase, ßTa2O5, undergoes an allotropic transformation at 1320o to 1350oC. 5-8 Four other oxides of tantalum have been reported. The oxides TaO2, TaO, and Ta4O have been reported by schonberg.9 A suboxide Ta2O, was observed by Wasilewski 6. However, the presence of oxides lower than Ta2O5 is questioned by Lagergren and Magneli.7 In oxidation studies, vermilyeal0 and Peterson, et al.,12 reported one possible phase intermediate between Ta and Ta2O5. Only Ta2O5 was formed in the tantalum air reaction, as reported by Michae1.l3 Several studies have been made on the kinetics of the tantalum-oxygen reaction. vermilyeal4 investigated the range 50° to 300°C and found that the rate of growth of a thin adherent oxide film could be described by the Cabrera-Mott theory. Gulbransen and Andrew15,18 studied the reaction kinetics of tantalum in oxygen pressure of 1/10 atm at 250° to 450°C. At all temperatures the reaction followed the parabolic rate law for periods up to two hours. The oxidation behavior in the range 500" to 1000°C was found to be linear at oxygen pressures of 0.2 to 600 psi according to Peterson. et al.l1 At very low pressures (1 x 10-3 to 2 X lo-' mm of Hg) Gebhardt and seghezzi17 reported linear oxidation at 800° to 1500°C. The reaction of tantalum with air is similar to the reaction with oxygen. Studies have been made by Waber, et a1.,12 and Michae1.l3 Two nitrides of tantalum, TaN and Ta2N are known. Their structures have been determined by Brauer and Zapp 18,19 The tantalum-nitrogen reaction kinetics have been investigated by Gulbransen and Andrews. 15, 16 The reaction follows the parabolic rate law at 500° to 850°C at a nitrogen pressure of 1/10 ,atm. At the same temperature, the tantalum-nitrogen reaction is much slower than the tantalum-oxygen reaction. EXPERIMENTAL TECHNIQUES Material— The material used in this study was high-purity, electron-beam-melted tantalum obtained from the Temescal Metallurgical Corp. The hardness of the as received ingot was 76 Vhn. The analysis of the material is given in Table I. Methods—Cylindrical specimens of tantalum approximately 0.9 cm in diam and 0.5 cm in length

Jan 1, 1962

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By William S. Springer

A NEW preparation plant has been put in - operation to treat coal from the recently opened Concord mine, located about 15 miles west of Birmingham, Ala., by the Tennessee Coal, Iron & Railroad Co., a U. S. Steel subsidiary. The mine produces metallurgical grade coking coal from the American seam for use as coke in the company's blast furnaces at the Fairfield and Enseley works. The capacity of the operation is 1000 tons of run-of-mine per hr, approximately half of which is delivered to the by-product coke plant at Fairfield after beneficiation to metallurgical grade. The remaining portion of the mine run is rock and refuse removed during preparation. No boiler coal or other fuels are produced by this mine. Preparation of the coal is done both under- ground and on the surface. The underground primary crushing station removes some tramp iron, and screens and crushes the oversize, most of which is rock, to protect the main slope conveyor. The surface plant consists of a crushing and screening plant, large blending bins, a two- process washing plant, a water clarification and

Jan 1, 1950

By AUGUSTUS J. MONKS, Norman L. Weiss

THE Santa Barbara Unit of the Compania Minera Asarco, of which the San Diego mill is a part, is in the Parral District of southern Chihuahua. Although the concentration of sulfide ores has been practised in Santa Barbara since 1900, the San Diego mill, completed in 1921, was the first plant in northern Mexico to attempt the treatment of oxidized lead ores. From the milling point of view the many ores that have been treated at San Diego are very similar, the differences among them being rather of degree than type. Since 1921 the number of ores from different sources treated simultaneously has varied from four to eleven; in no case have any distinctive characteristics warranted the separate treatment of any of these. The zone of oxidation, source of the ores milled at San Diego, extends to a depth of 300 to 400 ft. below the surface. These ores carry more gold and less silver, lead, copper, and zinc than the underlying sulfide ores; the gangue minerals appear comparatively unchanged by oxidation and leaching. Lead occurs in diverse minerals, chiefly in cerussite, galena, and angle-site, the proportion of the lead in galena varying considerably in the different mines. An average of the feed to the mill would show the following approximate distribution of the lead content:

Jan 1, 1930

By R. B. Fuller, E. T. Casler

MANY changes were made in the methods and equipment used in the mining of pebble phosphate rock in the generation immediately preceding the present World War and it would be extremely interesting to note the improvements that will be made during the next generation. Literally, much water has gone over the dam since the days when we used local cordwood for generating steam and drying pebble phosphate rock. belt-driven centrifugal pumps operated by steam engines. and floating dipper or centrifugal dredges; when we removed overburden by small steam shovels and transported it by dinkey locomotives and six-yard cars; when washing machinery was installed on wooden structures the washers being replaced every four to six years. Those were the days when men were plentiful, and 47 different mining companies were selling their products, based on .decidedly meager information; and. like so many mining operations, little thought was given to conservation. As the importance of phosphate rock has become more prominent in the thoughts of our economists, a more intelligent approach has been made to mining problems. Vast improvements have been made in the technique and processing of the phosphate matrix and stripping of overburden, which, in turn, have brought developments in machines and equipment and a more

Jan 1, 1944

By E. W. Pehrson, J. W. Furness

NONMETALLIC MINERALS, exclusive of fuels, may be divided into three groups: Building materials, fertilizer minerals, and miscellaneous minerals. Building materials, such as sand, gravel, slone, lime, and the ingredients of cement and clay products, occur widely in nature and are thus available near consuming centers at relatively low prices. Cost of transportation over great distances deters any' substantial movement in world trade. On the other hand, fertilizer minerals, such as phosphate rock, potash, nitrates, sulfur, and pyrite, and the miscellaneous nonmetallic minerals, such as long-fiber asbestos, mica, graphite, fluorspar, and china clay, do not have such widespread occurrence and consequently contribute the major part of the world's commerce in such minerals. The U. S. Bureau of Mines has prepared charts showing the inter-

Jan 1, 1936

By A. O. Dady

PRODUCERS of both bituminous and anthracite coal have for many years been worrying about the gradually decreasing consumption of their product in the United States. Twenty years ago production had climbed to a peak of 569,000,000 tons of bituminous and around 90,000,000 tons of anthracite. In 1939 it was about 393,000,000 tons of bituminous and 51,000,000 tons of anthracite. This does not mean that the country is using less polver than it did twenty years ago, or that we are living in colder buildings. As a matter of fact, about three times as much electric power is now being consumed as in 1920. In general two factors are responsible for the drop in coal consumption: (1) greater efficiency in the use of coal, and (2) increased competition from hydro power, internal-combustion engines, and substitution of oil and gas for coal in conventional furnaces. As to the first factor, it took 3 Ib. of coal to generate a kilowatt-hour of electricity in central stations in 1920 and it takes 1.4 Ib. now; it took about 175 Ib. of coal in railroad locomotives to haul 1000 long tons a mile in 1920 where it talces about 120 lb. now: and marked economies have also been made in the use of coal in steel plants: in by-product coke ovens, and in other large uses. As to the second factor, three times as much electricity is produced from water power now as was produced in 1920; three times as much oil is being consumed in various ways; and likewise, the consumption of natural gas has tripled- whereas coal consumption in the same period has dropped by 40 per cent

Jan 1, 1941

By E. W. Pehrson, J. W. Furness

THE method of presentation in the accompanying charts is based upon the well-known formula: production plus imports minus exports equals apparent consumption. Thus for each area for which data are shown there are two columns of equal height, one representing production plus imports, the other apparent consumption plus exports. Usually no account has been taken of increases or decreases in stocks. All columns and flow lines are drawn to a linear scale which is supplemented by figures showing the actual quantities represented. Owing to the small area occupied by the European countries on the world map it was impossible to show the details of the trade of the individual countries. All of Europe (except Russia), therefore, is shown as a single unit. However, statistics of production and consumption indicated elsewhere on the charts show the degree of self-sufficiency enjoyed by the major European powers.

Jan 1, 1936

By P. Payson

INTERGRANULAR corrosion in corrosion-resistant chromium-nickel steels has been widely discussed in the last few years. So far as the author knows, nothing has been published which definitely shows that this tendency can be eliminated, although suggestions have been made that a remedy is possible if certain specifications are satisfied. Strauss, Schottky and Hinueber1 suggested an increase in chromium content to an extent that would prevent the impoverishment of chromium on carbide precipitation sufficient to cause impaired corrosion resistance in the matrix. Pilling2 suggested an increase in nickel, so that the stability of the austenite matrix would be increased. Aborn and Bain,3 say that "intergranular attack-may be eliminated by preventing carbide precipitation (e. g., by lowering the carbon content or somehow raising its solubility) or by precipitating it permanently under conditions which will not remove chromium from solid solution so drastically at any points." In a later paper Aborn and Bain4 state that many different metallic elements, tungsten, vanadium, copper, aluminum, molybdenum, titanium and zirconium, have been added in small per-centages to increase the stability of these alloys, but that it has been reported that according to the copper sulfate test these added elements act only to retard the intergranular corrosion, and that increased nickel and chromium contents have similar effects. Newell5 showed that the lower the quenching temperature before reheating, the less severe was the intergranular attack.

Jan 1, 1932

By T. L. Joseph

The extent to which hot metal from the blast furnace affects open-hearth practice and the quality of steel produced has been discussed widely. Open-hearth operators have attributed difficulties experienced in making satisfactory steel to characteristics of the pig iron not disclosed by ordinary analysis. The commonest criticism of the iron has been that it is "physically cold" or "dirty." Often when the blast furnaces are working irregularly the quality of the iron is questioned. A cold hearth, slipping and hanging, the use in the past of unsintered flue dust, and the use of ores difficult to smelt have been associated with the production of iron of poor quality. The difficulty of the situation is that we have no proven yardstick for quality aside from ordinary analysis. Uniformity in analysis is recognized as being important, but the difficulty of changing the open-hearth practice when the iron analysis varies widely may not always be fully appreciated. Although the problem of correlating the characteristics of steel with those of pig iron is admittedly obscure, the effort of producers of quality steel to investigate all factors that may have a bearing on the final product is justified. This report contains data on the oxides in several hundred casts of basic iron produced in a furnace during the course of normal operation on Lake ores. Incidental to the study of the oxides in the iron, it was desirable to follow closely the temperature of the iron. The effect of temperature of the iron upon the silicon and sulphur present is discussed. A general relation between the basicity of the slag and the sulphur in the metal was developed. The amount and composition of oxides in the hot metal and in the steel bath during various intervals between melt-down and tap are discussed. Heats of rimmed steel, killed steel, and semikilled steel were investigated. The hot metal on individual heats was either all taken from a mixer or consisted partly of direct metal and partly of metal from the mixer. Samples of the iron for oxide determinations were

Jan 1, 1937

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By G. L. Schroeder

Investigations were conducted at two underground locations, foreman's room and 5702 area, of the Kermac Nuclear Fuels Corp. uranium mining installation, Ambrosia Lake, New Mexico. The rock environment is stratified sandstone. Pressures were varied from minus 0.4 an Hg to plus 3.8 cm Hg with respect to barometric pressure, and were maintained for periods ranging from several hours to 21 days. One cm Hg overpressure (-1.5% of normal barometric pressure) produced a 20-fold decrease in Rn flux into the foreman's room as compared to the Rn flux observed during dilution ventilation. The 5702 area experienced a 5-fold decrease in Rn flux for a similar overpressure. During 21 days of continuous 1 cm Hg overpressure in the 5702 area this reduced Rn flux was maintained. The smaller reduction in flux for the 5702 area results in part from the proximity of the foreman's room to a non-pressured area and the presence of an impermeable shale lens overlying the ceiling of the 5702 area. A 0.4 cm Hg underpressure of the 5702 area increased the Rn flux into the area by 3-fold over the non-pressured value. A barometric pressure influence on Rn flux into the mine and on air Rn concentrations in non-pressurd areas of the mine was measured. A falling barometric pressure causes an increase in the flux of interstitial gas into the mine; a rising barometric pressure decreases this flux. These effects are not seen in overpressured mine areas. Radon concentrations in rock interstices show, during overpressure, decreases of all locations monitored except in the immediate vicinity of the shale lens above the 5702 area ceiling. These reductions are the result of air flowing from the mine into the rock interstices under the influence of the pressure gradient induced by the overpressure. The relative humidity of the 5702 area was reduced after 2 days of 1 cm Hg overpressure from a pre-overpressure value of 96% to 81%. The control of harmful or noisesome gases which emanate into underground mining areas from surrounding rocks is often a costly necessity. In uranium (U) mines this problem is presented by the high interstitial concentrations of radon-222 (Rn), a radioactive noble gas of 3.82-day half-period, formed in the decay scheme of U238, and the relative ease with which this noble gas diffuses from its parent rock into the interstices of the rock and then to a working area. Long-term exposure to moderate concentrations of Rn (3000 µµc per 1) and its short-lived alpha-ray emitting daughter products, RaA (Po218) and RaC (po214), has been found to result in an increased incidence of bronchial carcinomaa2 The acceptable limit of Rn daughter products in a mine atmosphere is presently set at a concentration of short-lived radon daughters which would be in equilibrium with 100 ppc of Rn per 1 of air. Ventilation of mines is conventionally accomplished by continuously diluting the mine air with fresh air brought in by fan or natural convection from above ground surface. The diluted air is allowed to vent freely to the atmosphere. This process does nothing to retard the rate at which gases (including Rn) diffuse into the mine from surrounding rock. It merely reduces the concentrations of these gases within the mine. It is suggested that in a sufficiently permeable rock environment a slight pressurization of the mine air may induce air flow from the mine into the interstices of rock surrounding the mine. The convective flow of comparatively fresh air will reduce the concentration and the concentration gradient of undesirable gases in the rock interstices adjacent to the mine. Radon will diffuse counter-current to this convective flow at a rate proportional to its concentration gradient. In time, a steady state of convection and counter diffusion will be established. The Rn flux into the mine will never be reduced to zero, and will only asymptotically approach zero as the overpressure (and hence the convective velocity of purging air) approaches infinity. During 1963 and 1964, an investigation into the effect which such applied pressures have upon the Rn characteristics of a mine atmosphere was conducted at the Kermac Nuclear Fuels Corp. uranium mines, Ambrosia Lake (near Grants), New Mexico.

Jan 1, 1967

By H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.' The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

By N. H. Emmons

An interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at its plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory. Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaccs. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top mas necessary and the engineering force was started on the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of east copper, but the heat was great that the copper bent readily, due to the jarring of its

Jan 1, 1911

By D. B. Hobbs, L. W. Kempf, R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13 per cent. of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 25S, Special 17S and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings. REVIEW OF LITERATURE The literature on the heat treatment of aluminum-silicon alloys is not very extensive. The following review gives the principal references of which the authors are aware, in which appreciable information may be found.

Jan 1, 1928

By R. Ehrlich, F. E. Crane

A consolidated porous medium is mathematically modeled by networks of irregularly shaped, interconnected pore channels. Mechanisms are described that form residual saturations during immiscible displacement both by entire pore channels being bypassed and by fluids being isolated by the movement of an interface within individual pore channels. This latter mechanism is shown to depend strongly on pore channel irregularity. Together, these mechanisms provide an explanation for the drainage-imbibition-hysteresis effect. The calculation of steady-state relative permeabilities, based on a pore-size distribution obtained from a Berea sandstone, is described. These relative permeability curves agree qualitatively with curves that are generally accepted to be typical for highly consolidated materials. In situations where interfacial effects predominate over viscous and gravitational effects, the following conclusions are reached. 1. Relative permeability at a given saturation is everywhere independent of flow rate. 2. Relative permeability is independent of viscosity ratio everywhere except at very low values of wetting-phase relative permeability. 3. Irreducible wetting-phase saturation following steady-state drainage decreases with increasing ratio of nonwetting- to wetting-phase viscosity. 4. lrreducible wetting-phase saturation following unsteady-state drainage is lower than fir steady-state drainage. 5. Irreducible nonwetting-phase saturation 101lowing imbibition is independent of viscosity ratio, whether or not the imbibition is carried out under steady- or unsteady-state conditions. Experiments qualithtiveIy verify the conclusions regarding unsteady-state residual wetting-phase saturation. Implications of these conclusions are discussed. INTRODUCTION Natural and artificial porous materials are generally composed of matrix substance brought together in a more or less random manner. This leads to the creation of a network of interconnected pore spaces of highly irregular shape. Since the geometry of such a network is impossible to describe, we can never obtain a complete description of its flow behavior. We can, however, abstract those properties of the porous medium pertinent to the type of flow under consideration, and thus obtain an adequate description of that flow. Thus, the Kozeny-Carmen equation, by considering a porous medium as a bundle of noninterconnecting capillary tubes, provides an adequate description of single-phase flow. With the addition of a saturation-dependent tortuosity parameter in two-phase flow to account for flow path elongation, the Kozeny-Carmen equation has been used to predict relative permeabilities for the displacement of a wetting liquid by a gas. 1-5 It has long been recognized that relative permeability depends not only on saturation but also on saturation history as we11.6,7 Naar and Henderson8 described a mathematical model in which differences between drainage and imbibition behavior are explained in terms of a bypassing mechanism by which oil is trapped during imbibition. Fatt9 proposed a model for a porous medium that consisted of regular networks of cylindrical tubes of randomly distributed radii. From this he calculated the drainage relative permeability curves. Moore and slobod,10 Rose and Witherspoon,11 and Rose and Cleary12 each considered flow in a pore doublet (a parallel arrangement of a small and large diameter cylindrical capillary tube). They concluded that, because of the different rates of flow in each tube, trapping would occur in one of the tubes; the extent of which would depend upon viscosity ratio and capillary pressure. They limited

Jan 1, 1970

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Jan 1, 1961

By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By W. L. Saunders

IMPORTANCE OF ROCK DRILLING. IT has been estimated that the value of the mineral products of the United States is about $2,000,000,000 a year; that about $25,000,000 is expended. annually for explosives and that about double this sum is paid in wages where blasting is done. The value of the mineral products does not adequately express the importance of the industry involved in the excavation of rock and ore because of the enormous sums of money expended in tunnel driving, in quarries, and in open-cut excavation generally. We know that the Catskill Aqueduct in the neighborhood of New York, which is now nearing completion, has cost some $165,000,000 and that about one-third of this may be rated as rock excavation. These illustrations are given in order to call attention to the great importance of an industry the extension and development of which in our industrial life depend so much upon the economics of rock drilling. Reference has been made to the new Catskill Aqueduct. There are three aqueducts leading into New York, each built at periods separated by some 20 years of time. 'The first one, known as the Old Aqueduct, conveys the waters of the Croton river to New York City in a manner which reminds one of the old Roman aqueducts, the ruins of which are still in evidence. The engineers who laid out these old conduits sought to direct their lines around the hills and into the valleys, at all times avoiding the rock. When it was necessary to cross a river or a deep ravine, a bridge or causeway was constructed. High Bridge, over the Harlem river, is an arched masonry viaduct differing in no essential features from the aqueducts of the Romans. When the second Croton Aqueduct was built, about the year 1890, the art of drilling rock had been so far perfected, and the use of explosives, through the invention of dynamite, had become ,so general, that this waterway was planned and executed on straight lines, following rather than avoiding the rock. The second Croton Aqueduct is a tunnel through rock, about 32 miles in length; material gneiss, almost as hard as granite. Its construction was made practicable by sinking

Jan 9, 1913

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

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

Jan 1, 1963