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By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By N. Brown

IT has been observed that a hexagonal-close-packed crystal will undergo the same macroscopic displacements as an isotropic material if the basal plane is perpendicular to the axis of twist.&apos; Other orientations may produce both bending and twisting, but this analysis will be confined to pure torsion of a right circular cylinder. The z axis, the axis of twist, and the specimen axis are coincident. The displacements are given by Uq = rz, Ur = Uz = 0 [1] where 4 is the angle of twist per unit length. This requires rotational slip, as discussed by Frank&apos; and Wilman, which may be observed readily. The relative rotation of adjoining slip planes is simply produced by a movement of a planar grid of screw dislocations."." The screw dislocations are of the same sign and they move radially inward. For hexagonal-close-packed metals, the grid is hexagonal and the screw dislocations lie in the < 2110 > directions. The displacement of a point is the resultant of two displacements produced by intersecting screws sweeping over the point. The dislocations must pass over the point (r, o) in such a manner that its resultant displacement corresponds to the observed macroscopic displacement. If 6&apos; is measured from the [1010] direction, then for 0 < ? < ~/3, only the [1210] and 121101 type screw dislocations are needed to produce the required displacement. If n1 screws of type [1210] and n2 of type [2110] pass over a point, then, in order that Ur = 0 n, sin ? - n2 sin (/3 — 6&apos;) = 0. [2] If the tangential displacement is to be independent of 0, then n1 cos ? + n2cos (/3 —?) = N [3] where N is independent of ? and thus depends only on r. Nb is the tangential displacement where b is the Burgers vector. Since U? is a linear function of r, then N must be a linear function of r. If a2 is the outer radius and a, is the inner radius to which the plastic deformation has extended, then N = Nm2 r-a1 [4] This function meets the conditions that at

Jan 1, 1956

By G. J. W. Kor, F. D. Richardson

The sulfide capacities a1 1500°C of slags in the systern CaO + CaF, +Al2O3 have been measured by bringing samples into equilibrium with gas mixtures made from CO + CO2 + SO, + N2. The capacities are negligzble both JOY CaF, and CaF, + Al2O3 melts but when lime is present even at 20 wt pct capacilies as high as 30 x lom3 can be obtained. The results have yielded information concerning the liquidus at 1500°C and fluoride-oxide melts in general. The slags used in electroslag refining contain substantial amounts of calcium fluoride. Robinson and Grainger&apos; report that good results can be obtained by using slags of the approximate composition 70 wt pct CaF2 + 30 pct Al2O3. It has also been reported2 that a mixture of 50 pct CaF2 + 30 pct A12O3 + 20 pct CaO makes a good slag for general use. In view of the fact that very low sulfur contents are claimed for ingots produced by the electroslag process. studies have been made of the sulfide capacities [c, = wt pct S (PO2/Ps2)1/2 at 1500°C. of slags consisting of pure calcium fluoride, and of its mixtures with lime and/or alumina. These studies have also provided information on the phase diagrams. The slags were brought into equilibrium with gas mixtures prepared from NZ + CO + CO2 + SO2. Because CaFz is volatile and also easily hydrolyzed. measurements were made of its loss in weight in various flowing gas mixtures. EXPERIMENTAL Procedure. The apparatus and procedure were the same as described previously. Both platinum and iridium crucibles were used (height and inner diameter about 1 cm), but those made from iridium were stronger and able to withstand a greater number of experiments. In each experiment two crucibles were set in an alumina support and 1 g of slag mixture was divided between them. The materials from each crucible were analyzed separately after being brought to equilibrium with the gas, and then quenched in the water-cooled end of the reaction tube. Materials. Alumina and lime were prepared as de-scribed previously.4 Calcium fluoride was obtained by igniting Analar calcium fluoride in a platinum boat at about 800°C in a stream of pure dry nitrogen: the product was cooled in a desiccator. The slags were produced from mixtures of the powdered constituents, these being melted together in the course of each equilibrium experiment. The sulfur analyses and the X-ray diffraction meas- urements on the solidified slags were made as described previously.4 From the latter it appears that the CaF2 contained less than 0.5 mol pct CaO. RESULTS Values of (ps2/po2) for the Gas Mixtures. The re-sults have been represented in terms of (ps, /Po,)"? for the various gas mixtures used. The va1;es of this function at 1500°C are listed in Table I: they were calculated from the data cited previously for calculations at 1350°C 4 Weight Losses with CaF, and CaF, + CaO. The re-sults of the weight loss measurements* at 1500°C for

Jan 1, 1970

MINING METHODS. JAY A. CARPENTER, Chairman P. B. BUCKY, Vice-Chairman CLYDE E. WEED, Vice-Chairman ROY A. HARDY, Secretary Alluvial Mining CLINTON BERNARD O. B. PERRY NORMAN CLEAVELAND C. M. ROMANOWITZ R. B. EARL! NO J. B. STAPLER BENERE H. GRANT CHARLES THURMAN Open-Cut Mining Iron A. D. CHISHOLM P. G. HARRISON G. E. DIEHL EARL E. RUNNER G. E. LEVEQOE

Jan 1, 1942

By J. Burns Read

IT IS the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnance Department, during the War, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Ordnance Department in obtaining these data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The manufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodicals and, therefore, will not be given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540° to 650° C. (1000° to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases are then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followed, by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430° to 480° C. (800° to 900° F.) by immersion in a salt bath or by gas flames. After being washed, the cases are tapered, when they are ready for machining, inspection, and testing.

Jan 4, 1922

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),&apos; while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).&apos; These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By Paul A. Beck, M. N. Parthasarathi

The vecrystallization texture. formed by selective growth of random nuclei in an 80 pct volled 99.997 pct A1 crystal of initial orientation mear (123) (41.21 was found to consist of components related to the single-component rolling texture by 40 deg. rota-tiows around [111]axes. The relative-volume fractiovz of the various recrystallization-texture componezts may be accouzted for 012 the basis of the Lou) mobility of twist boundaries, if it is assumed that the mobility of the tilt boundaries also varies with their orientation. Similar results with a, aluminum-alloy cystal of the (110) [112] orientation, containing iron, silicon, and zinc, show that these solute contents do not impair the effectivezess of the oriented growth mechanism of re cry s-tallization- texture formation. In a previous investigation1,2 it was found that a sharp recrystallization texture is formed as a result of the oriented growth of random artificial nuclei in an aluminum crystal rolled to 80 pct RA, on the (110) plane in the [ 112] direction. Four recrystallization-texture components were found to occur, with orientations corresponding to 40-deg rotations around [111 1 axes of the deformation texture. Reorientations of this type were already found in earlier work,3,4 where the presence of random nuclei could be reasonably assumed, but was not rigorously documented. The same orientation relationship was found also by Lucke and Liebmann, who actually measured the orientation dependence of boundary-migration rates in the recrystallization of A1 crystals slightly deformed in tension.5,6 The occurrence in the recrystallization texture of only four of the eight crystallographically equivalent orientations of the type referred to above remained unexplained,1,2 although it was clearly not a result of the absence of suitable nuclei. Recently Burgers7 suggested that this effect may be due to the aniso-tropy of boundary mobility observed2&apos;6; it was found that the recrystallized grains of the 40-deg [111]-rotated type grow much faster in directions perpendicular to the [ 111] they have in common with the matrix than parallel to this direction, i.e., the tilt boundaries have much higher mobility than the twist boundaries. The four orientations corresponding to

Jan 1, 1962

By Francis B. Foley

In examining steel under the microscope, one is constantly confronted with structures that are difficult to interpret. Recently, in a collection of samples for exhibition purposes, the writer found a piece of open-hearth runner metal, 2 in. (50 mm.) in diameter, that had been fractured for use as a sample of cast-steel structure. On polishing and etching a section for the purpose of photographing a field to typify the microstructure of steel in the "as cast" condition, a variety of structures was found (Fig. 1) so arranged as to arouse interest at once. For a distance of about 0.065 in. (1.6 mm.) from the skin of the runner, normal ingot structure was found (Fig. 2); this was followed by a zone, about 0.215 in. (5.5 mm.) wide, of considerably lower carbon content in which occurred a most pronounced Widmannstattian structure (Fig. 3); from this point on to the center of the runner, the metal was again of normal ingot structure (Fig. 4). Representative samples taken from the metal in the three zones showed the following analysis: Carbon Nickel Chromium Per Cent. Per Cent. PeR Cent. Metal from skin........................... 0.34 1.26 0.63 Widmannstattian zone.................... 0.21 1.18 0.63 Metal from center......................... 0.34 1.32 0.67 Such a condition might result from decarburization followed by recarburization of the skin. This section came from one of the branch runners to the bottom of the mold, not from the main runner, and it is difficult to conceive of decarburization occurring in this portion of a runner. If the metal were stripped while quite hot, some oxidation would take place but the recarburization is unaccounted for. It could not occur by segregation after solidification—the tendency then is for diffusion and homogeneity. The following seems to fit the conditions and is offered as an explanation. The outside layer of normal structure 0.065 in. (1.6 mm.) thick was chilled on the walls of the runner brick when the molten metal first entered the runner. As the molten metal flows by, the outside of the stream

Jan 1, 1920

By H. E. Rorschach

Oil-field activities in Oklahoma made 1936 the best year since 1930. Approximately 2800 wells were completed, an increase of about 20 per cent over 1935. Purchasers&apos; reports filed with the Corporation Commission showed a total of 200,240,252 bbl. of oil purchased from leases in 1936. The assembly of a complete table of the oil fields of the state was not achieved, as many of the early records of operators and pipe-line companies are not complete, and data for the older fields will perhaps never be fully tabulated. Table 1 includes all of the new fields and most of the important fields of the State of Oklahoma. The outstanding developments of the year were: the discovery of rich Wilcox-sand production in the Moore pool; the spectacular drilling campaign in the Capitol or Mansion extension in the Oklahoma City pool; the surprising extension of the Olympic pool and the Hunton lime zone in the Fitts pool; and the failure to find more Ordovician production in southern Oklahoma. Wildcat discoveries, which were on a par with 1935, resulted in the discovery of such promising pools as Billings-Wilcox, North Bethel, North Earlsboro and North Lucien. The Fitts-Upper Simpson, Edmond, Jesse, Keokuk Falls and South Burbank pools underwent considerable development. Fitts Pool.—The Fitts area in Pontotoc County was greatly extended during the year and was the leader in drilling activity in the state. The producing limits were pushed to the east and north and the development of the Hunton lime horizon was outstanding. In the Upper Simpson zone 162 wells were completed; 137 in the Hunton lime zone and 26 in the Wilcox zone. The Oil Creek zone, a sand body below the Wilcox member, was discovered by the Magnolia-Statler No. 3 well located in the 1/4. 1/4 of sec. 28-2N.-7E. Moore Pool.—The Moore pool, in Cleveland County, which was opened in 1935 by the Sinclair Prairie-Franklin Community No. 1 well, surprised the oil industry when the Sinclair Prairie-Marvel No. 1 well, on Apr. 1, 1936, discovered a rich body of Wilcox sand below the distillate

Jan 1, 1937

By Frederic Benard

RECOVERY of selenium and tellurium at Copper Cliff by the Ontario Refining Co. has been previously described by the writer.1 During 1935 a new building was erected to house this operation and description of the new plant and process form the subject of this paper. The building, of modern steel and tile construction, covers an area of 5900 sq. ft. with a volume of approximately 165,000 cu. ft. The large monitored center bay is flanked by two smaller outside bays, one of which is devoted to the tellurium section. All equipment, ceilings and upper walls, are treated with aluminum paint, giving good illumination and facilitating good housekeeping, essential from a health standpoint in handling material of this nature. EQUIPMENT Layout and type of equipment conforms to the requirements of the process as described below. In the selenium section, storage tanks, neutralizing tanks and precipitators are of steel construction, lead-lined and. arranged for gravity flow (Fig. 1). The neutralizing tanks are equipped with water-cooled lead coils for controlling solution temperature, agitation being accomplished with compressed air. The precipitators are provided with mechanical agitators, and sulphur dioxide is introduced into the solution through 3-in. lead pipes leading from a manifold attached to the cover of the precipitator. Each precipitator has internal cooling coils and an air-jet exhauster to carry off fumes. Neutralized solutions are filtered in a 29-plate wooden filter press using heavy cotton duck as a filter medium, forced feed being maintained by a Welmet centrifugal pump. Dilute solutions are concentrated by evaporation in a vacuum evaporator, constructed of cast hard lead. Heat is supplied by an outside steam chest operating under 15 lb. steam pressure. The solution is circulated through the steam chest by a pump of antimonial lead at a rate approximating 400 cu. ft. per min. The evaporator is evacuated by a water-jet condenser that creates a vacuum of 26 in. of mercury under normal operating conditions. The capacity of the vessel is 60 cu. ft. and the rate of evaporation 25 cu. ft. per hour.

Jan 1, 1938

By C. S. Anderson

Georgia, since 1829, has produced nearly $18,000,000 from her gold mines, but in late years the output has dwindled to insignificance. In view of present universal efforts to increase gold production, it seems pertinent to record some recent observations in that field, briefly review its past and weigh probabilities of reviving gold mining there. Little in this paper can be claimed as new or original, and it does not present results of a detailed or profound investigation of the whole region. The Allatoona gold mine was reopened in January, 1932, and explored at greater depth during the period from January to June of that year. A number of other abandoned mines were visited, but since the workings, in common with most such mines in Georgia, were flooded or caved, underground conditions could not be examined. For a wider knowledge of the subject, a search was made through available pertinent literature and statistics, a bibliography of which is appended hereto. To all the sources obligations are gratefully acknowledged. Production The discovery of gold in Georgia, in 1829, led to an influx of 6000 to 7000 miners and a production of over $200,000 in the following year. A branch of the United States Mint, established at Dahlonega in 1838, accounted for $6,115,569 up to the time of the Civil War. The output fluctuated greatly from year to year, with an all-time peak of $582,782 in 1843. In only one other year, 1845, was the half million mark exceeded. After the war mining began again, but 1883 is the last year for which an output of $200,000 is reported. Placers, always the main source of production, were yielding less and less, and in spite of increased quartz-mining activities the downward trend continued. The last year in which there was a production of $100,000 was 1902. In 1914, $16,270 came from 26 placers and 11 deep mines, with the latter reporting 1750 tons of $3 average value. In 1925, one placer and four lode mines that mined 8100 tons assaying $1.19 per ton produced $9500. One placer and one quartz mine, operating in 1930, reported a total output of $4194. Table 1 pictures the waning output.

Jan 1, 1934

By AIME AIME

The Institute Headquarters at Spokane was established at the Spokane Hotel, and included a Bureau of Information for the benefit and comfort of members and guests of the party during the time of the meeting. The first session, held Tuesday afternoon, Sept. 28, 1909, in the beautiful Convention Hall ,of Masonic Temple, was called to order by Mr. E. J. Roberts, Chairman of the Spokane Local Committee, who introduced Mr. J. C. Ralston, City Engineer, representing the Mayor of Spokane and the Spokane Chamber of Commerce. Mr. Ralston extended to the members and guests of the Institute a cordial welcome to the city of Spokane, substantially as follows:

Dec 1, 1909

By Theodore Swann

DURING recent years, there has been a material increase in the use of ferrophosphorus in the steel industry. It has been observed, when rolling sheets, that those made of Southern iron did not have to be rolled at as high a temperature as the others and, consequently, did not stick together. The reason was found to be the phosphorus content of Southern iron. It was therefore thought that an addition of phosphorus to sheet steel of other than Southern origin would give the same result as the use of Southern iron. At first, this addition was made by intro¬ducing phosphate rock in the blast furnace and reducing it together with the iron ore; but, because of the necessity for only small quantities of this grade of iron, the process was not satisfactory. The manufacture of ferrophosphorus was then introduced, so that additions might be made to the open-hearth furnace or ladle. Ferrophosphorus was first manufactured in the blast furnace. This method, however, can only economically produce a grade of product up to about 20 per cent. To produce a higher grade, it would be necessary to charge a larger proportion of phosphate-bearing material; and as the rate of absorption by the iron is low, there would be an increased loss of phosphorus oxides. This feature makes the production of a higher grade ferrophosphorus in the blast furnace uneconomical. The use of high-grade ferrophosphorus in the steel requires a smaller addition and involves, besides the economies in handling, an additional economy in transportation. The alloy with a higher percentage than 20 per cent. can be made only in the electric furnace. In the ordinary operation of the electric furnace in the production of ferrophosphorus, an alloy may be produced containing 26 per cent. phosphorus; this is the limit, for it does not seem possible to produce a higher phosphorus alloy even if large excesses of phosphatic materials are used. The reasons for the difficulty in raising this percentage of phosphorus are not known. The compounds Fe3P, containing 15.6 per cent., and Fe2P, containing 21.7 per cent. phosphorus, have been studied and it appears as if the alloy produced, containing percentages of

Jan 10, 1924

By Betty J. Laswell, Gerald W. Laswell

Rotary drilling in modern open-pit mining is usually considered the lead phase which not only establishes the production rates but frequently limits them. From this viewpoint alone, the drilling phase must be maximized. The drill phase is the step that permits all the other operational phases to function within their design limits. This means that, in most cases, the drill is literally run to destruction to ensure that the shovel will be able to smoothly and consistently load a manageably size muck, the haul trucks can carry a balanced load without having a boulder dropped through the bed, and the crusher can devour constant rock size.

Jan 8, 1978

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-&apos;. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.&apos; and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner&apos;s3 data for cation self-diffusion, D:, using Wagner&apos;s theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner&apos;s data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-&apos; at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By Victor L. Stevens

The Oso tunnel is one of three tunnels located on the San Juan-Chama Project in south-central Colorado. The purpose of the tunnel is to carry water from the upper San Juan watershed through the Continental Divide into the Rio Grande watershed. The Oso tunnel contract was awarded by the U.S. Bureau of Reclamation to a joint venture of Boyles Brothers Drilling Co., Gibbons & Reed Co., and Cimco in February 1966. The Oso tunnel is 26,660 ft long and has a rock section of 10 ft, 2 in. with a lined diameter of 8 ft circular. The main portion of the rock formation was in the Lewis shale. This formation is quite consistent in hardness and texture with exception of localized limestone concretions and sandy siltstone inclusions. The job was bid on the basis of using a James S. Robbins mole of the P221 series. The decision for using a mole was predicated on the geology and the experience of the same joint venture on the adjoining Azotea tunnel where a mole was successfully used. The Robbins P221 series mole is capable of cutting from 9 ft, 11 in. to a 10 ft, 7 in. diam without any major change. It is 40 ft long and weighs 60 tons. The cutting head has 22 disk-type cutters and one center pilot (standard 9 7/8 -in.) tricone bit. The head is powered by four 75 hp electric motors. Gripper pads at about the midway point on each side of the machine are pushed into the tunnel ribs and thrust-cylinders in front of each gripper apply pressure to the face as the head rotates. The regripping cycle is 3 ft and then the grippers are retracted and advanced. Each cutter on the perimeter of the head is followed by a bucket which scoops up the cut material, almost in the same manner as a water wheel, and dumps it into a conveyor situated along the top of the mole. The muck from the mole conveyor is dumped into a gantry-type conveyor. The gantry conveyor is 350 ft long and is pulled

Jan 1, 1970

By R. E. Heithecker

Almost every oil well drilled into limestone formations in Kansas is treated with hydrochloric (muriatic) acid upon completion: to increase potential capacity of well and thereby increase its "daily allowable" production; to shorten time required to produce recoverable oil; and to increase quantity of oil recovered ultimately from reservoir. Acid treating marked a forward step in the producing fields of Kansas; in fact, many old limestone fields that almost had reached their economic producing limit were "rejuvenated" with acid and their capacities to produce increased several times. It also caused a marked increase in the ultimate oil recovery of some old and nearly depleted fields of Kansas. The effect of the acid was due to the cleaning-out action by the acid at the face of the limestone, the enlargement of the small drainage channels, and the apparent penetration of the acid to previously undrained porous and saturated strata. Studies of the effects of acid were made in the Fairport field, three groups of wells in the El Dorado field and the Shutts field. Estimation of increased recoveries resulting from acid in these fields and groups of wells ranged from 1000 to 2400 bbI. per acre. Limestone structures that had been tested by drilling and found noncommercial were later completed as commerical oil-producing formations through the use of acid. The Kansas City formation, Valley Center field of Kansas, is an example. Increased oil production and revenue from the old fields justified the reconditioning of equipment, which in most cases had become in poor mechanical condition. The first treatment with hydrochloric acid of an oil well in Kansas was in October 1932, and by the end of 1937 almost 6000 wells had been treated. Many wells were treated more than once and the total number of treatments exceeded 8000 by the end of 1937. Approximately 12 3/4 million gallons of acid was required for these treatments. The report includes 15 illustrations and 16 tables.

Jan 1, 1939

By R. E. Heithecker

Almost every oil well drilled into limestone formations in Kansas is treated with hydrochloric (muriatic) acid upon completion: to increase potential capacity of well and thereby increase its "daily allowable" production; to shorten time required to produce recoverable oil; and to increase quantity of oil recovered ultimately from reservoir. Acid treating marked a forward step in the producing fields of Kansas; in fact, many old limestone fields that almost had reached their economic producing limit were "rejuvenated" with acid and their capacities to produce increased several times. It also caused a marked increase in the ultimate oil recovery of some old and nearly depleted fields of Kansas. The effect of the acid was due to the cleaning-out action by the acid at the face of the limestone, the enlargement of the small drainage channels, and the apparent penetration of the acid to previously undrained porous and saturated strata. Studies of the effects of acid were made in the Fairport field, three groups of wells in the El Dorado field and the Shutts field. Estimation of increased recoveries resulting from acid in these fields and groups of wells ranged from 1000 to 2400 bbI. per acre. Limestone structures that had been tested by drilling and found noncommercial were later completed as commerical oil-producing formations through the use of acid. The Kansas City formation, Valley Center field of Kansas, is an example. Increased oil production and revenue from the old fields justified the reconditioning of equipment, which in most cases had become in poor mechanical condition. The first treatment with hydrochloric acid of an oil well in Kansas was in October 1932, and by the end of 1937 almost 6000 wells had been treated. Many wells were treated more than once and the total number of treatments exceeded 8000 by the end of 1937. Approximately 12 3/4 million gallons of acid was required for these treatments. The report includes 15 illustrations and 16 tables.

Jan 1, 1939

By F. A. Forward, A. H. Ross, J. Halpern

IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to +15oC. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO3 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi O2. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1958

By R. L., Fullman

During the past year there have been a number of significant investigations that have furnished evidence on the driving forces governing grain growth and on the role played by boundary impurities. Thus Burke has shown that in high purity alpha brass the rate of grain growth in the earliest stages is approximately inversely proportional to the existing grain size. This relation agrees with one derived by Zener assuming that surface energy was the driving force in grain growth. Also in confirmation of the surface energy hypothesis, Burke found that growth virtually stopped when the grain boundaries or even only the grain corners were melted.

Jan 1, 1949