Search Documents

By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By James Terry Duce

The symposium on production for the year 1940 contains few papers on the foreign situation. It is probable that the foreign part of next year's symposium will be even shorter. This is due to rigid censorship in various countries, as the question of the volume of petroleum supplies has become one of great strategic importance. This is even more true than in the last war, owing to greater mechanization of armies. 'It has always been the policy of officers in charge of the symposium to refrain from publishing information that might possibly injure national or private interests. At the close of the war we hope again to publish full and accurate records of production abroad. Excerpts from Circular to Authors In order to facilitate interpretation of the data in this chapter, we print the following excerpts from the Circular to Authors. The field is the unit in this tabulation. In cases of fields extending across State boundaries, such as Rodessa, it is suggested that each State author treat the section of the field in his State as a unit, and by a footnote indicate that the field extends into an adjacent State. Each space in Table I may represent one of four possibilities; either it is not applicable to the particular field, or the proper entry is not determinable, or the proper entry may be determinable but is not determinable from data available to the author, or the proper entry is determinable. When spaces are not applicable, leave blank; in spaces where the proper entries are determinable but not de-terminable frod data available to the author, please inserty; in spaces where the proper entries are determinable by the author, make such entries. y implies a hope that in some future year a definite figure will be available. The entry of a zero is a positive declaration, and an important declaration where it is in order. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In sucli cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces the correct entries represent the opinion of the author (for example, "Area Proved') and in such cases the entry need not be hedged to such extent as when the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. It is thought that the nearest whole numbers are sufficiently accurate for our purposes except as to percentage of sulphur in oil. If an author desires to report any other figures to tenths, he may do so. The quantity of gas produced should include, where possible, gas sold or otherwise marketed, and gas blown into the air, burned as flares or otherwise wasted. Segregation of these figures would be interesting if the authors can make such segregation. In any event, the figures should represent as nearly as possible the total quantity of gas removed from the reservoir. Under the columns on "Depth," the average depth to the top of the productive zones and to the bottom of the productive wells, when

Jan 1, 1941

By Raymond B. Ladoo

Wollastonite is a calcium metasilicate, with the formula CaSiO3; containing theoretically 48.3 pct CaO and 51.7 pct Si02. It is one of many natural and synthetic silicates with varying CaO/SiO2 ratios, with and without water of crystallization. While it is a very common mineral, deposits of sufficient size and purity to be of commercial interest are unusual. There is only one producer (1958) of wollastonite for industrial use in the United States, Godfrey L. Cabot, Inc. at Willsboro, New York. There has been a small production of surface material for ornamental use from near Blythe, California. Carload tests have been made on California wollastonite for making mineral wool and a commercial plant for this purpose was projected in 1957. Properties Wollastonite is monoclinic and commonly occurs in masses or aggregates of bladed or needle-like crystals. It has a perfect cleavage parallel to the long prismatic axis. It is rather brittle and some types grind easily to a very finely fibrous product, but other types, due to interlacing of fibers, are tough and difficult to grind. Mobs hardness is 4.5 to 5; specific gravity 2.8-2.9; index of refraction 1.616 to 1.631; melting point 1,512°C. Color when pure is a brilliant white, but when less pure it may be gray or brown. Luster is vitreous, transparent to translucent. Common mineral associates are garnet (several varieties), diopside, calcite and quartz. The nature of the mineral impurities determines to a large degree the commercial value of a deposit. At Willsboro, New York, the impurities consist chiefly of iron garnet and iron diopside which are both magnetic and so are easily removable by magnetic separation, yielding a nearly theoretically pure product. Some deposits in California contain calcite and quartz which cannot be removed cheaply, thus limiting market possibilities. Occurrence Wollastonite is a contact metamorphic mineral occurring in most places within or associated with impure limestones. The deposits at Willsboro, New York1,2,3,5 consist of two or more beds dipping 15-50°E and striking NW-SE. The main bed, 30 to 70 ft thick, may be traced on the surface for at least 2 ½ miles. In this belt, the Pre-Cambrian Grenville limestone has been injected and partially replaced by the more liquid portions of an anorthositic magma. Buddington and Whitcomb3 have described the rock as "Mixed gneisses, pyroxenite and garnetiferous gneisses and skarns." Prospecting revealed the wollastonite at ten different places in the belt, overlain in most places by a garnet rock. Diamond drilling has proven several million tons with probable reserves around 15 million tons. Interbedded with the wollastonite are beds of garnet from a few inches to several feet in thickness. In the wollastonite ore itself the chief and almost only associated minerals are garnet (mostly almandite but some andradite and grossularite) with small amounts of green hedenbergite. Inasmuch as the almandite and diopside are magnetic they are easily separated from the wollastonite in high intensity magnetic separators. If grossularite should occur in quantity other means of separation would be needed. Wollastonite has been reported at 35 localities in California12 but only those in the Big Maria and Little Maria Mountains, 16 to 20 miles north of Blythe, Riverside County, are

Jan 1, 1960

By S. S. Clarke

The sheet-ground deposits of the Tri-State district, because they are fairly uniform in thickness (7 to II ft.)—rather flat, with an easy dip to the west—and cover a large acreage, offered a problem of improved transportation. Heading advance in this kind of mine is very rapid and track haulage requires a larger crew of trackmen than do other mines, and a heavy investment in track. The use of some type of rubber-tired truck equipment for underground haulage was under consideration for some time by the Eagle-Picher Mining and Smelting Co. The nature of some ore bodies made them not adaptable to truck haulage and some mines that did offer possibilities were equipped with other types of haulage, and the expected savings by the use of trucks did not offset the loss of investment that would be incurred in discarding other equipment. The decision was made to sink a new shaft, designed for skip hoisting, on the Blue Goose ore body, and then develop truck equipment. Developing Tractors and Trailers A study was made of internal-combustion engines for power units in the tractors, but the extreme difficulty of controlling air circulation, and the heavy cost of drilling large churn drill holes for blower installations, led to the adoption of a tractor with a storage battery. The storage-battery tractor that was on the market for mine haulage was impossible to obtain because all were needed for defense work. Several standard electric-truck chassis were purchased and rebuilt in the Eagle-Picher shops. The steering wheel was shortened and set vertical, permitting the driver's seat to be moved forward, and the frame was shortened enough to take the battery box and the fifth wheel support that carried the gooseneck of the dump trailer. The fifth wheel, or turntable, is of the ball and socket type. Tig. I shows the ball fastened to the gooseneck. The socket is split to permit introduction of the ball and is held by through-bolts, and the socket is welded to a ½-in. plate, which in turn is attached to the tractor frame. Smaller wheels and tires were put on to reduce over-all height. If it had been necessary, the spring: could have been reversed, or taken off entirely, to gain additional clearance. The tractors are equipped with 48-cell, 23-plate, 400-A.H. batteries. With the initial tonnage and mileage, the batteries were about 50 per cent down at the end of a shift. Tractors have truck tires 7.50 by 20, 8-ply, front and rear, the rear being dud. After four months of use, the .tires are beginning to show signs of failure.* In

Jan 1, 1943

By B. D. Cullity, S. S. Hsu

The stress distribution at the surface of a twisted cylinder is analyzed along the boundary of a slip plane of arbitrary orientation and this analysis is applied to the torsion of cylindrical crystals of magnesium. A criterion for slip is developed and the critical resolved shear stress of magnesium in torsion is found to be 0.038 kg per sq mm. The mechanism of torsional deformation in magnesium and aluminum is described, as well as the relaxation of a twisted crystal at elevated temperatures. THERE has been considerable fundamental study A of the mechanism of slip occurring during deformation in tension and compression but comparatively little attention has been paid to the mechanism of torsional deformation. This paper is concerned with the way in which a single crystal deforms in static torsion and with the phenomenon of untwisting which a twisted crystal undergoes during annealing. Particular attention is paid to the application of the critical resolved shear stress law to torsional deformation. Probably the most likely mode of torsional deformation that can be imagined consists of rotation of one part of the crystal relative to another on the active slip plane. Here the most interesting feature is the slip direction. If a cylindrical single crystal is twisted about its axis and if, to consider the simplest case, the active slip plane is normal to the specimen axis, then the direction of gross slip at any point must always be at right angles to the radius drawn to that point. It follows that the crystallographic direction of slip must be continually changing, in sharp contrast to slip in tension which occurs in a crystallographically constant direction. Extensive investigations of slip in torsion have been made by Gough and his associates.' They made torsional fatigue tests on metal single crystals belonging to a number of different crystal systems and observed, with a microscope, the appearance of slip lines on the surface and of strain markings on the transverse cross section of cylindrical specimens. They concluded that the critical resolved shear stress law was just as valid in torsion as in tension, in the sense that slip occurred on that plane and in that direction in which the resolved shear stress was a maximum. They also established that the operative slip planes and directions were the same as in tension. They did not, however, measure the critical resolved shear stress in torsion nor, in fact, did they establish that a critical value of the resolved shear stress was necessary for the initiation of slip. Their investigations were, moreover, restricted to torsional fatigue tests which necessarily involve small strain amplitudes. Wilman,' studying crystal growth and the abraded surfaces of crystals, observed crystal fragments

Jan 1, 1955

By J. F. Poland

Location of Basins and Geologic Features of Occurrence: The major ground-water resources of California occur and are stored in the many large alluvium-filled valleys of the state. The deposits of Quaternary age which hold the ground water commonly are called valley fill. Meinzerl has discussed the characteristic features of this fill and showed that for western United States its distribution is concentrated chiefly in western Utah, Nevada, central Oregon, California, southern Arizona, and central New Mexico (see fig. 1). For California the principal ground-water basins are shown on fig. 2. Except for the Mojave Desert and the "Basin and Range" Valleys (fig. 2, Nos. 23 and 23A), which are not shown individually, the basins outlined on fig. 2 contain all the large reservoirs in valley fill within the state. The Sacramento and San Joaquin Valleys (fig. 2) together comprise the Great Central Valley of California, which has an area of about 18,000 square miles. The Sacramento Valley contains about 5000 square miles of valley lands, approxi- mately equal to the area of Connecticut; the San Joaquin Valley embraces about 13,000 square miles, equivalent to the areas of Massachusetts and Connecticut combined. Both the area and the ground-water use in the Central Valley is far greater than for all the other shaded alluvial basins of fig. 2 added together. Except for the Sacramento Valley, all the major ground-water basins of the state are south of Sacramento. The valley fill in these ground-water basins has been transported by streams and most of it has been laid down in alluvial fans, producing the typical alluvial-fan structure of aquifers radiating as tongues from a prismatic pile of coarse, permeable debris at the canyon mouths; these aquifers are encased down slope by poorly sorted materials consisting of a clayey matrix with imbedded pebbles and boulders, interbedded with flood-plain silt. In the deeper inland structural valleys, the alluvial deposits interfinger at depth in the valley bottoms with horizontally bedded lacustrine sand, silt, and clay. The San Joaquin Valley is a good example. In the coastal valleys exposed to the sea, such as the Los Angeles coastal plain, the alluvial fans pass coastward into lagoonal and thence to shallow marine deposits. In all these basins, the gravel is coarsest and most permeable near the apexes of the fans, but tongues or lenses of clean gravel and sand may extend for many miles down the fan. Thus, these water-bearing structures are in a position to absorb stream flow near the canyon mouths and to transmit it through the buried radiating conduits.

Jan 1, 1951

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations'j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.' Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.' Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini's work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By S. Ramachandran, R. G. Woolery

INTRODUCTION Union Carbide is currently operating an in-situ leach project on the Palangana Dome area in Duval county. This deposit meets all the requirements for in-situ leach in that the ore (1) is below the water table, (2) is in a permeable horizon, (3) is amenable to chemical leaching, and (4) is confined by impervious layers. This project has been under commercial production since 1976, and its capacity has been expanded on three occasions since going on-stream. Recently, additional uranium reserves were discovered on the Rogers-Cardenas (R-C) property about 32 km north of the Palangana operation. The ore is located within the Oakville sands and its characteristics are quite similar to those of the ore at Palangana. Both are an unconsolidated Arkosic sand high in clay and calcium carbonate. The R-C ore, however, is somewhat coarser with a mean particle size of 0.15 mm as compared to a mean particle size of 0.07 mm for the Palangana ore. In all respects it would appear that this ore would be a candidate for in-situ leach as a satellite operation to Palangana. Unfortunately, R-C ore is above the water table and, therefore, not amenable to the Palangana practice. Because of the limited known reserves in this deposit, it is readily apparent that conventional mining and milling are out of the question. However, because of its proximity to our Palangana operation, it seemed worthwhile to consider other options. The most viable route based on our past experience was to heap leach the ore. Our recent success at our Gas Hills facility and our Maybell operation, in employing a heap leach practice to our marginal reserves seemed to be a logical approach for processing this ore. Our experiences at both locations are described in "Heap Leaching - A Case History" by R. G. Woolery et al., Mining Engineering, March 1978. In both instances the process is an acid leach circuit and acid consumption averages 20 kg/t H2SO4. A preliminary feasibility study showed that because of the high strip ratio required for the R-C project to be successful, additional ore reserves must be located and that a method of heap leaching with an alkaline circuit would have to be developed. As a result of this paper study, the decision was made to proceed with a program of additional exploration drilling to determine the total ore reserves that could be mined economically. The Mining Department will evaluate each ore zone for cutoff grade, strip ratio, and expected mining cost. At the same time, a laboratory program to evaluate the available core samples for amenability to heap leaching with respect to an estimate of uranium recovery and processing costs was developed. This program is currently in progress, and at this time, we are just completing our process amenability study. BENCH-SCALE EVALUATION OF THE R-C ORE The initial bench-scale slurry leach tests on the R-C ore showed an acid consumption in excess of 200 kg/t H2SO4. These data, of course, discouraged us from considering this process route. Not only would the acid cost be prohibitive, but the gypsum generated by the reaction of the sulfuric acid with the calcium carbonate of the ore would severely effect the percolation of the lixivant. For this reason, the laboratory program was directed toward an alkaline circuit compatible with heap leaching. Because of the proximity of the R-C property to our Palangana operation, it seemed advisable to integrate the processing of this ore into the production at Palangana. Doing so would enable us to bring the R-C property into production by merely enlarging our present facilities at Palangana; otherwise, construction of a grass roots plant would be necessary. Ideally, the simplest method would be to construct the heaps at Palangana and employ an ammonium carbonate/bicarbonate leachant compatible with the in-situ production liquor. The product liquors could then be co-mingled or processed separately as desired. To determine if this goal was practical, samples of the R-C ore were obtained, and a laboratory program initiated. Heap leach amenability testing consisted of preliminary bench-scale evaluation to determine optimum solution strength and ultimate uranium recovery, followed by small column tests to confirm the bench-scale metallurgy and to determine percolation characteristics. These bench-scale tests are being followed by pilot-scale testing approximating field conditions. As expected, the bench-scale tests showed that the dissolution rate is considerably slower for alkaline leach than has been our experience in acid leaching. Because of the slower reaction rates, product liquor grades will be lower than for acid, as greater volumes of solution are required for satisfactory uranium extractions. The greatest influence on reaction times found in the laboratory was the carbonate/bicarbonate strength and oxidant addition. However, the higher salt concentration reduced the efficiency of the IX resin circuit and about 25g/L salt proved to an upper limit compatible with subsequent IX treatment. The oxidant contributed significantly to the early extraction rate but seemed to have only minimal effect on the total practical U308 extracted or the time required to achieve it. This variable will require larger scale testing to determine if the added cost of the oxidant is actually justifiable. Thus, the small-scale laboratory slurry tests, based on the 0.088% U308 sample available, indicate that leaching at 25g/L ammonium carbonate/bicarbonate, with or without oxidant, we might expect an 80-85% U308 extraction on this ore.

Jan 1, 1979

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By Whitman E. Brown, Louis J. Erck

The installation in 1948 of a Hum-phrey~ spiral concentrator section at the Hill-Trumbull plant of The Cleve-land-Cliffs Iron Co. is the latest commercial method on the Mesabi Range being used for the recovery of fine iron ore. In two stages of concentration 84 spirals treat approximately 120 long tons per hour of minus ? in. ore. These spirals augment the production of the heavy-density plant which recovers the plus 36 in. iron from the plant crude ore. Structure of the ore is such that, when crushed, about 50 pct of the plant crude is minus ? in. size. After de-sliming in a 66 in. Akins classifier, grinding the classifier product in a ball mill and again desliming in a 78 in. Akins classifier about 15 pct of the crude ore remains to be treated in the spiral plant. Overall recovery of the ball mill feed in the Hill-Trumbull spiral plant during the 1948 season was about 53 pct of the weight and 66 pct of the total iron content. Of the actual feed delivered to the spirals from the 78 in. classifier 64.9 pct of the weight was recovered containing 73.7 pct of the total iron. The average analysis of the spiral concentrate is 55.05 pct Fe and 14.83 pct SiO2. An average of mill assays during the 1948 season is given in Table 1. The Hill-Trumbull plants treat both wash ore and jig-type ore. During the 1948 season spirals were used only on the fine sizes of jig-type ore. At times the deslimed minus ? in. size is of sufficient grade to warrant bypassing the spirals but in the main the fine size is delivered to the 48 first stage spirals and thence to the 36 cleaner or second stage spirals. In the past several years numerous Mesabi Range ores in the fine size cate- gory have been tested by a wide variety of beneficiating equipment. The prodigious amount of research devoted to the recovery of values in the fine ore reflects the dire need of the iron industry to squeeze the last possible unit of iron from the mined ore and to develop suitable equipment and processes to satisfactorily concentrate the leaner horizons as they are encountered in the process of mining. Large governmental and private appropriations have been allotted, new laboratories built, research and technical staffs increased, and operator-manufacturer cooperative agreements applied to hasten the solution of the problem. The University of Minnesota, at its Eighth Annual Mining Symposium in January 1947, dedicated as its objective the bringing to light of technological developments in iron ore beneficiation. Papers were given at that time relating to processes being developed. Specifically, these papers reviewed flotation, Baum jig, selective media concentrator, Hardinge concentrator, Dorrco sizer, heavy media concentration, Hydrotator, and the Humphreys spiral. The Cleveland-Cliffs Iron Co., after encouraging results from tests in a small pilot plant using one full size spiral, made the first commercial installation of Humphreys spirals on the Mesabi Range at their Hill-Trumbull mine, Taconite, Minn. This company

Jan 1, 1950

By John A. E. M. Church

THE prospector's pan was the first implement used for saving gold, and its action is so effective that it has never been equalled for thorough work. Copper plates, blankets, sluices, and amalgamators of several patented designs have thrust it aside, but in spite of all the advances made there is no dispute among experienced men as to the comparative thoroughness of the work done by it and its rivals. When its rivals are doing their best, the pan can take their discarded refuse and prove their inefficiency by producing from it not only gold, but even the mercury which has been lost from the machines themselves. The trouble with the pan has always been that it was only a tool. Man was the machine that moved it. His work was high-priced, the quantity treated small, and it was impossible to use the pan for any but the richest sands. As a consequence the best gold-saving appliance known has been discarded for years and replaced by machines of inferior excellence, but which could more than make up for their limited ability in saving gold by their capacity for treating great quantities of ore. Mr. Peck is one of the old-time amalgamators of the Comstock district, and the first idea of the new machine came to him as he used to pan below the tailrace of his mill. No matter how fine the work of the mill was, the pan invariably proved that better could be done. The tailings always contained gold, silver, and mercury. This state of things is just as true to-day, after all the improvements that have been made, as it was then, and the much-vaunted method of the " Washoe process" consists in extracting 72 per cent. of the gold and silver by one operation, and then repeating this operation half a dozen times to get out about one-third of the remainder. With all the advances of twenty years in milling, there is nothing more crude in metallurgy than the treatment of tailings in many of the large mills of the West.

Jan 1, 1880

By John A. Church

Jan 1, 1880

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1'3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967

By W. F. Mullen, C. W. Stickler

WITH few exceptions, unit operations in the Pennsylvania slate industry in 1950 did not differ appreciably from production methods described by Behrel and Bowles2-4 several decades ago. Many traditionally picturesque but relatively inefficient hand operations continued to contribute to high operating costs in an industry in which the margin of profit, for various reasons, was admittedly low. As part of a general program in which the Pennsylvania State College has been assisting the slate industry to solve some of its problems, time and method studies were used in an effort to determine the bottlenecks of production flow. The results are as applicable to other stone industries as they are to slate. A study of the basic elements in the production of roofing slate, structural slate, and slate blackboards among selected slate producers revealed comparatively few refinements. Any marked difference in operating method was characterized largely by the available equipment, a noticeable difference in the working properties of the rock quarried by a particular company, and by either the habit thinking or ingenuity of the individual operators. With the hope that significant economies in manufacture might result, all the unit operations were broken down into elements for study and analysis. The greater part of the study encompassed those operations from the quarry rim to the finished product; however, to obtain a reasonable synthesis of time allotments per operation, several analyses of quarrying from the finish of the wire saw cut are included for reference. The complete study of quarrying made by Bowles several years ago resulted in the introduction of the wire saw into the operation; there appears to be a need for as fundamental a change in the processing of finished slate as the wire saw was in the quarrying process. Fig. 1 illustrates the flowsheet of quarried rock from the parent bed to the quarry rim with the basic elements which contribute to the difficulty of removing slate from the ground. In Pennsylvania roofing slate is produced by one of three procedures, many operations of which are quite similar. In the traditional or classical method the quarried rock is reduced by sculping and auxiliary manual treatment to workable size and then is split and dressed (trimmed to size) in the conventional shanty. Archaic as this method might appear, there are several elements that result in substantial savings over more mechanized operations. In a modified version of this method, the block is reduced by sawing and gouging preparatory to splitting and dressing in indoor stations. This method is particularly adaptable to rock which fractures unevenly by conventional sculping methods. In the third and more modern method, reduced block received from the block maker is diamond-sawed to length and finished on a production line. Fig. 2 illustrates the flow pattern in each case. In the modified and more modern plans, dressing is done on mechanically-operated trimming machines, which appreciably reduce the fatigue factor of the operator. However, it should be noted that it is advantageous for the operator to be able to control the speed of the knife to prevent breakage of certain classes of stock. In the classical plan the splitter and dresser normally act as blockmakers also and carry their eighter slabs (equivalent in thickness to eight shingles) into the shanties themselves, all of which adds to fatigue and reduced efficiency. The extremely low investment and operating expense of the classical method has undoubtedly been of paramount importance in its continuation. Production of Mill Stock The production of mill stock is accomplished by less picturesque methods than enter into the production of roofing slate but it is, in the main, relatively more efficient because of the increased use of machinery for handling and for finishing. Mill stock can be classified into two categories as far as difference in production method is concerned: structural slate and blackboards. The significant difference in operation is caused largely by the nature of the rock used for each product with the best and easiest cleaved rock being reserved for blackboards to permit the splitting of large slabs to as little as 1/2 in. in thickness. Structural stock, on the other hand, is split into panels no thinner than 11/2 in. and

Jan 1, 1952

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By A. L. Slaughter

The Homestake mine, located in western South Dakota, was discovered in 1876. The first reported production was in I 878. Total production through 1965 is 6,554,249 troy ounces of silver and 27,961,276 troy ounces of gold, worth $987,000,000 at present prices. Precambrian sedimentary formations at Lead total 20,000 feet. The Poorman Formation, the oldest, is chiefly ankerite carbonate. The Homestake Formation is iron-magnesium carbonate. The younger formations are argillaceous with some quartzites. The Cambrian Deadwood Formation unconformably overlies the Precambrian. All are cut by Tertiary intrusives. Sideroplesite schist of the Homestake Formation was converted to cummingtonite schist in the zones of higher-grade metamorphism. The Precambrian rocks show the effects of extreme isoclinal folding. A second stage of folding ( cross folds) may have been caused by the Tertiary intrusives. All folds plunge to the southeast. The Homestake ore bodies are pipe-like replacements of the Homestake Formation in zones of cross folding. It is believed that dilatation of the schists has increased permeability in these zones. Chloritization of the schists is the most widespread effect of the mineralization which is divided into four stages. Principal minerals of the first stage are quartz, chlorite, and arsenopyrite; in the second stage, quartz, ankerite, and pyrrhotite. In the third stage only pyrrhotite was deposited. The fourth stage followed the intrusions of Tertiary dikes and deposited mostly pyrite and calcite. Gold accompanies all stages and is always the last mineral to be deposited. It is most closely associated with arsenopyrite of the first stage but can be interpreted as having been deposited during the fourth stage and superimposed on the products of the earlier stages.

Jan 1, 1968