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By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By C. L. Thornburg

FLANKING the Valley of Mexico on the northeast is a mountain range known as the Sierra de Pachuca. This northwesterly-trending range is about 30 miles long and 5 miles wide, its summit attaining an elevation of more than 10,000 feet above sea level, or 2000 feet above the valley floor. Pachuca, a town of 50,000 inhabitants, lies nestled at the southwest base of the range, 60 miles northeast of Mexico City. Three miles to the east, just over the summit and on the northeasterly slope, is the mountain town of Real del Monte with a population of about 20,000. These are the two principal towns in a 40-sq mile area whose yield has brought the district to its high rank among the world's silver producers. Total production probably exceeds 1.25 billion ounces of silver and 4.5 million ounces of gold. Exploitation by the Spanish was under way by 1530. As the mines were deepened operations became handicapped by the inadequate method of handling water with horse whims and bull skins. To offset this disadvantage a two-mile drainage tunnel was started in 1749 and completed ten years later. John Taylor of London acquired the mines from the third Count of Regla in 1824 and formed the Compania de Real del Monte y Pachuca. Two years later Cornish pumps were brought from England. A Mexican company purchased the British interest in 1848 and within a few years resumed an old project of driving a second, lower three-mile drainage tunnel, completing it in 1857. After Americzn interests acquired control of the property in 1906 operations expanded to an unprecedented scale, despite periods of political strife, unstable prices, labor problems, and a growing burden of taxation. An idea of the scale of operations may be gained from records of the last two decades prior to 1947, the last year for which production information is at hand, during which time production ranged from 1.4 million to 1.1 million tons per year, and the combined development and exploration, exclusive of diamond drilling, amounted to about 18 miles annually. Pachuca differs from Zacatecas and some other Mexican silver vein districts that flourished and de- clined in earlier centuries in that a substantial part of its total production was made after 1900. While the district's accelerated activity in this century was largely due to the successful application of the cyanide process to the treatment of the ores, improved pumping methods, and new mechanical equipment, it was at the same time stimulated by the opening up of important new orebodies as a result of active and extensive exploration of the vein system. Some of these orebodies were found on veins which terminate upward far below the surface, and though these particular veins do not crop out, they show relationship with a type of alteration which may be their surface expression. The district has been studied by many able geologists, and a large store of information has been accumulated, much of which is recorded in published as well as private papers. Wall Rocks Extrusive Rocks: The Sierra de Pachuca is a thick accumulation of Tertiary eruptive rocks consisting mainly of flows, breccias, and tuffs. Numerous recognizable volcanic vents within the range itself manifest that the range was built up by material ejected from these vents. The maximum thickness of the volcanic pile is not known, but from deep exploration and from relationship with Mesozoic sediments to the north and east it is inferred that the average thickness in the main part of the district may be at least 6000 ft. The extrusive rocks comprise four general types, which in ascending order of age are: andesite, rhyolite, dacite, and basalt. The veins are confined largely to the andesite, the dominant rock of the region. Characteristically this rock is augite andesite, but it includes comparatively acidic as well as basic layers, the acidic strata being

Jan 1, 1953

By D. R. Mash

A strong yield point with attendant enhanced mechanical properties was found in commercially pure beryllium under certain conditions of heat treatment. Beryllium specimens also responded to both quench and strain aging treatments. Based on these results, a possible means of obtaining increased normal temperature mechanical properties is suggested. COMMERCIALLY pure beryllium has been found to exhibit the yield point phenomenon and several other aging manifestations under certain conditions of heat treatment. This behavior is not surprising in view of the present accumulation of experience regarding such effects in numerous metals; but in addition to extending this experience to include beryllium, the present study is of interest because aging effects are generally associated with the presence of small amounts of solute elements. The well known lack of tensile ductility in beryllium at normal temperatures is also considered to be due to impurities in some way. In the present investigation, the view was taken that beryllium of commercial purity (greater than 98 pct) should be considered as a dilute alloy and that precipitation phenomena may well exist which could lead to enhanced mechanical properties. In connection with this possibility, published data on the variation of mechanical properties with temperature are of interest. For example, Fig. 1 illustrates the variation of ductility (percentage of elongation) and ultimate strength as a function of temperature for beryllium of various histories.* Although these curves are somewhat schematic in nature, they clearly indicate the possibility that precipitation of an unstable phase and/or aging effects occur during tests in the region 400" to 700°C. The existence of such behavior should be recognized as affecting the properties of the commercial material and perhaps can be employed advantageously. Experimental Method All testing was done at room temperature using a Baldwin universal testing machine. A microformer extensometer was used in conjunction with a micro-former-type stress-strain recorder. All tests were conducted at constant loading rate, the slowest rates being used. This corresponded to 120 lb per min in the 1200 lb full scale range and 300 lb per min in the 6000 lb full scale range. After the rate of loading was set in the elastic range of the material during the early part of the test, no further adjustments were made, allowing the test to proceed at that setting. In the plastic region of the curve above the yield region, strain rates of from 0.002 to 0.006 in. per min were regularly obtained. All experimentation was carried out on specimens machined from the same lot of beryllium, lot No. Y5036BP. Table I shows the chemical analysis as furnished by the supplier, Brush Beryllium Co., as well as the standard specifications to which commercial beryllium is produced. Both 1/4 in. thick hot pressed plate and ½ in. round hot pressed and warm extruded rods were obtained. The history of the material is reported to be as follows: 1—Beryllium metal plates, produced from a standard hot pressed QMV beryllium metal block 4x15x40 in., were cut off and finished machined to 1/4x6x12 in. flat plates. The original hot pressed block was made by hot pressing —200 mesh vacuum cast attri-tioned powder at about 1050°C under vacuum. 2—Beryllium rod was hot pressed and warm extruded. Extrusion billets were machined from the regular hot pressed blocks followed by extrusion at 425°C. The extrusion was done without jacketing, and graphite was used as a lubricant. The rods were then straightened at 720 °C, after which they were annealed at 800°C for 15 min. Both flat tensile specimens and round tensile specimens were tested. The former were machined from the plate stock into standard specimens according to specifications shown in ASTM E8-52T. The nominal cross-section was 0.25x0.500 in. and the gage length was 2 in. The round specimens were

Jan 1, 1956

By P. Somasundaran

Flotation of minerals has usually been discussed in terms of solid-liquid interfacial phenomena. This paper discusses the relative importance of phenomena such as collector adsorption at other interfaces formed between the bubble, liquid and solid. Adsorption of collector ions of various chain lengths at liquid-gas and solid-gas interfaces has been obtained. The data have been analyzed under conditions corresponding to those of flotation to show the significant role of collector adsorbed on the bubble surface in determining the bubble-mineral attachment required for flotation, and consequently to suggest consideration of this role in the development of better flotation conditions. Vacuum flotation of quartz with alkyl ammonium acetate reported in the foregoing paper1 showed that the collector chain length has an effect on flotation even at concentrations below those necessary for hemi-micelle association of the hydrocarbon chains at a solid-liquid interface. This chain length effect might be explained by the following arguments: Hydrocarbon chains find it energetically favorable to be in a medium of low dielectric constant. Considering the possibility of an iceberg structure at the solid-liquid interface, such a structure would produce a region of lower dielectric constant at the solid-liquid interface than in the liquid phase, because the dielectric constant of ice is 2 to 3,2 while that of water is 80. Depending on chain length, this difference will certainly cause even individual ions to adsorb in higher quantities at the solid-liquid interface. Another mechanism to consider is the possible formation of dimers, trimers, etc and chain length would influence this formation. But, above all, the chain length effect on flotation at concentrations of low adsorption at the solid-liquid interface could be due to the significant but often-neglected role of the collector adsorption at the bub- ble surface. Collector ions or molecules are adsorbed both at the solid-liquid interface and the liquid-gas interface. Below the concentration for hemi-micelle association at the Stern plane adjacent to the surface, the bulk of the collector ions adsorbed at the solid-liquid interface are in the diffuse part of the double layer. If such systems, where there is a gas bubble coming in contact with the solid surface, are to achieve some degree of electroneutrality, those collector ions would have to migrate from the diffuse part of the double layer to the region directly adjacent to the surface during the induction period when the bubble is making contact with the solid. The time necessary for this migration would contribute to the induction period required for creation of the solid-gas interface. It seems reasonable that the induction period could be reduced sufficiently for flotation to occur if these collector ions were carried to the surface by the bubble. In an attempt to ascertain whether or not the bubble could possibly have sufficient collector ions at its surface to meet the requirement mentioned above, the adsorption density of the collector ions at the liquid-air interface was determined. For this purpose, the surface tension of alkyl ammonium acetate solutions was determined as a function of concentration. Adsorption densities of the collector at the liquid-gas interface were calculated using the Gibbs adsorption equation: where y is the interfacial tension and ri and pi are the adsorption density and the chemical potential, respectively, of the chemical species, i. Using the convention that the adsorption density of water at the interface is zero, the following relationship is obtained for the liquid-gas interface where lg refers to liquid-gas interface and RA+ refers to the alkyl ammonium ions. For dilute solutions, rf^-wri^&rfwW [3] where C is the concentration of the collector ions in solution. l?:: can now be evaluated using Eq. 3 and surface tension measurements.

Jan 1, 1969

By R. H. Frazier, C. H. Lorig, F. W. Boulger

This investigation establishes the effect of ferrite grain size resulting from various heat treatments on the transition temperature of a semikilled steel plate. Different austenitizing temperatures and various cooling rates were used. The ductile-brittle transition temperatures were determined by the Navy tear test and the keyhole Charpy test. THE data presented in this paper deal with quality characteristics of ship-plate material which were investigated in a research project sponsored at Battelle by the Bureau of Ships, Dept. of the Navy. Specifically, the object of this investigation was to establish the effect of ferritic grain size (resulting from various heat treatments) on the so-called transition temperature of ship-plate steel. Transition temperature is not a fixed property of steel. It is derived from a series of static or dynamic tests made at various temperatures and is qualified by specifying the type of test employed as well as the testing criteria. Because in earlier investigations of ship-plate quality1,2 the so-called Navy tear test and standard notched-bar tests (keyhole Charpy) proved to be useful in interpreting instances of brittle behavior of ship plate in service, these tests were used in the investigation reported in this paper. By definition,' in the Navy tear tests the highest temperature at which one or more of four specimens breaks with a brittle fracture (that is, when less than 50 pct of the fracture area has a dull fibrous texture) is termed "transition" temperature. In the Charpy tests, the 12 ft-lb level of energy absorption was used as a criterion indicating the "transition" temperature, although other levels of energy absorption were also used for comparison. Earlier work" on ship-plate steels indicated that the temperature at which ship plate is finished has a very significant effect on its notched-bar properties. Plates rolled in the laboratory, where the finishing temperature can be carefully controlled, showed a 16°F decrease in tear test transition temperature when the finishing temperature was lowered 200°F (from X" to Y°F). The same plates showed a drop of 10°F in the keyhole Charpy transition temperature from the same decrease in finishing temperature. Commercially finished plates' exhibit a similar trend. When the ferrite grain size of the hot-rolled laboratory plates was determined, a close relationship was found between the ferrite grain size and the notched-bar transition temperature." " he indicated relationship between grain size and transition temperature was in agreement with the findings on low carbon steels of Hodge, Manning, and Reichhold' despite the differences in composition of the steels. The cooling rate after rolling varies from one steel plant to another. This variation changes the micro-structure" and appears very likely to affect the notched-bar properties of the steel plates. In the investigation summarized in the present paper, heat treatments simulating finishing practices in the hot rolling of ship plate were used in order to vary the ferritic grain size. It is believed that the indicated relationship between grain size and transition temperatures of the ship-plate material will prove useful in estimating the effect of rolling temperature and of cooling rates from rolling temperatures on the notched-bar properties of semikilled steel plate. Material The semikilled steel plate used in this investigation was a ¾ in. hot-rolled plate from an open hearth heat. Other plates from this heat have been used on many other studies performed for the Ship Structure Committee," "," and the heat has been identified as project steel "A". The chemical composition of the plate1 was 0.25 pct C, 0.49 pct Mn, 0.011 pct P, 0.045 pct S, 0.04 pct Si, and 0.004 pct N.

Jan 1, 1956

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff' have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By Wallace W. Wilson

This DaoerAA calls to attention for the first time, to the writer's knowledge, a purported recovery of oil by substantially horizontal gas cycling that is considerably in excess of 50 per cent of the oil originally in place. The average angle of dip along the path of travel of the gas is less than one degree of arc. The best recovery by gas cycling previously brought to the writer's attention1 occurred in the case of the Mile Six Field in Peru, where about 68 per cent of the original oil in place has so far been recovered. In this case, however. the recovery was greatly aided 1)y the high dip angle of about 17.5". An approximate estimate of recovery was made by the method developed by the writer' for the case of the Cook Ranch Field, using an average relative permeability ratio function dictated by past experience with a number of good quality sandstones. A result of about 40 per cent recovery of the original oil in place wa* obtained after the 8.5 pore volumes of cumulative gas cycling undergone by the Cook Ranch Field. Tile writer desires to emphasize what appears to him as the sound engineering practiced at Cook Ranch, and also the care attending the taking of data and the high quality of the calculations made. It is impossible to take issue on factual grounds with any of the conclusions drawn in the paper. It is, however, desired to point out the difficulty of explaining the unexpectedly favorable oil recovery on ordinary theoretical grounds. It would be of interest to know whether relative permeability ratios have been measured on the Cook sand. The operator is inclined to attribute some of the excess benefit to settling of the oil across the bedding planes into the lower part of the sand. It is difficult for the writer to appreciate the importance of such an effect, inasmuch as the concomitant opening of excessive vacated pore space in the upper part of the sand would he expected to cause excessive bypassing of the gas. REFERENCE 1. Welge. H. J.: "A Simplified Method for Computing Oil Recovery by (Gas or Water Drive." Trans. AIME, (1952), 195, 91. AUTHOR'S REPLY TO MR. WELGE Welge has poined out clearly the difficulty of applying material-balance procedures in calculating the Performance of low-pressure, dispersed gas injection operations. There can be no argument that even with the most favorable assumptions of K,/K,, and with cumulative gas cycling in excess of normal expectations, the calculated oil recovery will be considerably less than the 72.5 per cent recovery realized from this project to Jan. 1, 1951. There probably are at least two reasons for the unusually high recovery from this reservoir, the effects of which would be difficult or impossible to calculate by known methods: 1. The operator did not use the same injection wells for the entire operation, and exercised considerable control over producing GOR by changing the locations of injection wells whenever well performance indicated excessive bypassing. Fifty-six wells were used for injection, not over 29 of which were in use simultaneously. This procedure resulted in frequent shifting of the fluid movement patterns in the reservoir and undoubtedly increased the ultimate recovery. The writer knows of no satisfactory procedure for calculating the effect of this practice. 2. Vertical movement of oil across the bedding planes of the reservoir rock hy gravity drainage tended to maintain a relatively high oil saturation, and hence a favorable K,/K, ratio, in the lower sections of the reservoir. As pointed out by Welge, this condition has aggravated the tendency for high producing GOR, but at the same time it has resulted in increased oil recovery. As may be seen from the performance charts for the various battery areas, operating (GOR'S have been quite high for the last several years of reported history.

Jan 1, 1952

By M. J. Hordon

Measurements of the 103 yield stress of ordered and disordered poly crystalline Cu ,Au were related to the ordered antiphase domain size determined by resistivity measurements. For undeformed material, a yield stress maximum wa obtained at a critical domain diameter of about 40A. Plastic deformation resulted in a marked increase in the yield stress and electrical resistivity of the ordered alloy compared to the disordered, the strain hardening rate increasing regularly with initial antiphase domain size. Order hardening was accompanied by a sharp reduction in size of the initially large domains. It has been observed that the yield stress of ordered and partially ordered Cu3Au alloy varies sensitively with antiphase domain size aid degree of order.ly2 In addition, ordering of the lattice leads to a marked increase in the strain hardening rate (order hardening) as compared to the rate for the disordered alloy. In the present investigation, changes in the electrical resistivity and yield stress of ordered polycrystalline Cudu with varying initial domain diameters were measured after tensile plastic deformation in order to examine the effect of cold work on the antiphase domain size. EXPERIMENTAL PROCEDURE Au-Cu alloy of 99.99 pct purity analyzing 50.85 wt pct Au-balance copper was obtained from the Handy-Harmon Co., N. Y., in the form of 0.061 in. diam drawn wire. Wire specimens 3 in. in length were given the following annealing treatment in nitrogen: 500" for 72 hr, 820" for 15 hr, and 450" for 5 hr, followed by a water quench. The annealing sequence resulted in a completely disordered structure with a grain size of about 0.2 mm. The disordered specimens were then reannealed at 360' in nitrogen for periods varying from 10 min to 150 hr followed by quenching to produce ordered structures with varying domain sizes. The degree of ordering and variation of domain size was followed by electrical resistivity measurements made at room temperature using a low resistance precision Kelvin double bridge apparatus. The specimen resistance was determined over a length of 4.0 cm between two brass knife-edge contacts while the specimen was immersed in an oil bath to minimize temperature variations. In addition, the current flow in the circuit was minimized by a current pulse technique in balancing the bridge in order to avoid heating the specimen. Using a sensitive galvanometer to detect the bridge null, the accuracy of the resistance measurement Wire specimens were plastically strained in tension with an Instron tensile unit at strain rates in the range 5 x 10"5 sec-' to 2 x 10"4 sec-'. Stress and extension data were fed into the Instron chart drive amplifier to obtain the actual stress-elongation curve from which the yield stress at 10"3 strain was determined. The maximum resolution of the apparatus was approximately 50 psi stress and 3 x 104 strain. At various plastic strain levels, deformation was interrupted and the electrical resistivity determined after removing the stress. RESULTS AND DISCUSSION 1) Yield Strength of Ordered Cudu. In order to determine the effect of the ordered antiphase domains on the initial yield stress, specimens were prepared with varying domain sizes ranging from zero for 5 completely disordered structure to about lo5A for a completely ordered structure by suitable annealing treatment. Domain sizes were estimated by comparing room temperature electrical resistivity data with the original data of Jones and sykes3 as modified by rdle.' In agreement with previous work, the resistivity varied sensitively with domain diameter and degree of order, decreasing from approximately 11.6 x l0- ohm-cm for the disordered structure to about 5.9 x l0- ohm-cm for ordered domains above 10"3 cm in diameter. Fig. 1 shows the change of the 103 yield stress with ordered domain size. It is evident that the maximum

Jan 1, 1963

By E. T. Hayes, A. H. Roberson, M. H. Davies

ZIRCONIUM has been produced on a pilot-plant scale for only a few years, but the potential uses have led a large number of research establishments to engage in a thorough study of the metal and its alloys. The work described in this paper is part of a cooperative project between the Bureau of Mines and the Air Materiel Command. The Zr-Cr system was one of the first investigated because of the possibilities of improving the properties at elevated temperatures, the chemical corrosion resistance, and the mechanical properties of zirconium in a manner similar to the enhancement of the properties of titanium by additions of chromium. There is no published work on the Zr-Cr system but from the similarity of the metals involved it was expected that it would be similar to the Zr-Fe' and Ti-Cr' systems. The materials used in this investigation were prepared in the Bureau of Mines laboratory at Albany, Ore. Zirconium was produced by magnesium reduction of zirconium tetrachloride, and a typical analysis is as follows: Fe, 0.06 pct; Ox, 0.08; N?, 0.01; C, 0.02; and other impurities such as Al, Pb, Ni, Ti, and Si less than 0.01 pct each. High purity chromium was prepared by treating crushed electrolytic chromium in a stream of dried and purified hydrogen." The resulting powder contained about 0.01 pct 0 and about 0.1 pct total metallic impurities. All alloys were prepared by arc-melting 50 g briquetted compacts of the desired composition in a Kroll-type" arc furnace using an inert atmosphere. The furnace was evacuated twice and backfilled with helium, which was gettered by melting a center zirconium button immediately before the alloys were melted. Alloys were remelted at least once to insure greater uniformity of composition and subsequently were annealed in vacuum at 1250°C for 48 hr. Fairly homogeneous alloys were obtained by this means; a slight loss of chromium from the surface by evaporation during the high temperature homogenization was noted. All alloys were analyzed for chromium and gave results in good agreement with the nominal composition. Spot checks on tungsten and nitrogen showed pick-up of these elements to be negligible. Over 70 alloys were prepared for use in this investigation; only the critical ones are shown in Table I. Alloys containing up to 10 pct Cr were amenable to hot working at 850°C and a number of these were sheath rolled to 1/16 in. thickness. Specimens were cut from the sheet for use as metallographic samples. For the thermal analysis a differential couple was used in conjunction with an X-Y recorder, the temperature of the specimen and the difference in ternperature between it and the standard nickel body were recorded simultaneously. Heating and cooling rates of 5°C per min were used. The sensitivity of the instrument was such that a difference in temperature between the specimen and standard equivalent to 0.1 mv produced a deflection of 1 in. on the recording chart. The chromel-alumel thermocouples were checked against a Bureau of Standards calibrated thermocouple. Melting-point determinations were made in a high vacuum induction furnace using an optical pyrometer. The pyrometer, calibrated against nickel, copper, and zirconium (iodide process) under near black body conditions, was focused on the base of a hole drilled in cylindrical samples. A North American Philips Geiger counter X-ray spectrometer was used for all diffraction studies. This instrument, in addition to supplying precise intensity measurements of planar reflections, has an added advantage in that metallographic specimens mounted in bakelite can be used directly, and this

Jan 1, 1953

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By Howard H. Fields

Any mining engineer with a desire to operate independently, with some financial backing, and with no fear of heavy responsibility and long hours, should be able to make a comfortable living in Mexico. Barring a few inconveniences such as a lack of satisfactory liability or accident insurance, the difficulty of obtaining repair parts or vehicles, and the length of time required to receive returns from shipments, the operation of small mine is not at all difficult. It is, in fact, a little easier to find a good prospect in Mexico than in the U.S.

Jan 1, 1950

By Max W. Ball

Our ever-increasing use of minerals has been the outstanding fact in our American economic development. The rise in our standard of living in the past century is without equal in human history. Nowhere in time or place has the man who works lived so well, or the man who cannot work been so well cared for. We live in a new world, even the poorest of us, that our forebears of 1849 could not have dreamed. That new world has come mainly from our use of minerals. Our per capita use of nonmineral products has grown too, but by only a modest amount. Food consumption per person has grown about 15 per cent in the past fifty years; lumber use per person ,has fallen 56 per cent and that of wood for fuel 65 per cent. Of all the products of field and forest, our use, per capita, may have increased by one fifth during the present century. In contrast, our per capita use of minerals has multiplied several times. Each of us uses 2% times as much steel and 16% times as much petroleum as our fathers used in 1900. In less than half a century our per capita consumption of all minerals has probably risen by 200 to 250 'per cent. Man once built with wood; today he builds mainly with brick and stone and steel. Once he traveled by the power of hay and oats; today he travels by the power of coal and oil. Rubber made from minerals is already better for some uses than rubber tapped from trees; before long it will be better for most and perhaps all uses. Even our ladies' graceful legs are clad in mineral fiber, where once animal or vegetable fiber would have covered them. Our high standard of living is a product of the machine.. The machine is made of minerals. The machine is driven by minerals. The machine age is a mineral age.

Jan 1, 1949

By L. H. E. Weyher

As a result of past developments, mainly at universities, the coal industry has had access for a decade or more to a number of computer programs for coal mine planning. Using some of these programs Bethlehem Steel's Research Department in 1969 launched jointly with Bethlehem Mines Corporation an extensive research and development program aimed at: (1) testing the capabilities of these programs through trial applications as the need and opportunity existed, (2) defining what additional capabilities were required to make mine planning computer systems fully useful in the hands of Bethlehem's mine-planning engineers in the field, and (3) developing and implementing in the field the mine-planning systems agreed on. This program is now nearing completion, and several of Bethlehem's operations routinely use the planning tools that were developed. The progress of this research program is discussed in terms of our initial trial applications of computer methods to mine planning and the incorporation of several innovative features into our new set of computer programs, in particular, the use of time sharing, data base management systems, and general-purpose simulation languages.

Jan 1, 1977

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

By R. L. Mauger, P. E. Damon

Potassium-argon dating of the late Mesozoic and Cenozoic intermediate to acidic plutons and volcanic rocks of Arizona and northern Sonora demonstrates the existence of two distinct magmatic episodes. The earlier episode begins in late Campanian time and dies out before the middle Eocene. Following a quiescent period in middle and late Eocene time, magmatism increases in Oligocene time, becomes most intense at the Oligocene-Miocene boundary and dies out as the Pliocene is approached. Pliocene magmatism is primarily confined to extrusion of post-orogenic basalts. The late Mesozoic-early Cenozoic magmatic pulse is essentially confined within the limits of the classical Laramide orogeny (Laramie through Wasatch time). The mid-Tertiary pulse is contemporaneous with the mid-Tertiary Basin and Range orogeny. The Laramide provides an excellent specific example of Umbgrove's concept of the pulse of the earth and in general his concept appears to be meaningful. Copper porphyry mineralization is time-congruent with Laramide magmatism and there seems to be no doubt as to the existence of a genetic relationship between the two phenomena. Two origins are tenable: direct accumulation of the copper sulfides in the copper porphyry liquid magmatic environment; or, introduction of the mineral constituents entirely from a larger source magma when the host rock is already crystalline. Transgression and regression of the epicontinental seas provide an excellent indicator of orogeny and epeirogeny. There was an overall transgression of the epicontinental seas from early Triassic time through the Turonian epoch in early late-Cretaceous time. Thereafter, there is a relatively continuous regression of the seas until the present time. Both the earlier transgressive episode and the later retreat are intermpted by temporary but distinct reversals. These interruptions can be correlated with classical orogenies. There are six distinct orogenies so indicated in the Mesozoic-Cenozoic eras. These occur at approximately 35 to 40 m.y. intervals. The regression of the epicontinental seas following the Turonian epoch was contemporaneous with the deepening of the Pacific ocean basin over the Darwin Rise. As the Darwin Rise was collapsing the East Pacific Rise was being elevated. The Western United States, situated on the eastern flank of the East Pacific Rise, was upwarped and tilted toward the east. Epeirogeny is the primary consequence of processes that operate on a global scale. Orogeny is an exothennic process that is limited in space and is treated here as a secondary consequence of epeirogenic-initiated warping. The off-campus buildings of the University of Arizona Geochronology Laboratories rest on the volcanic rocks of Tumamoc Hill. From this hill, the observer may obtain a beautiful view of typical Basin and Range topography. The city of Tucson lies below, contained within the broad Santa Cruz basin and surrounded on all sides by characteristic NW-SE trending ranges towering as much as 7000 ft above the valley floor. Since the senior author arrived in Tucson eight years ago, a great deal more has been learned about the geochronology of this and neighboring basins and ranges. For example, the volcanic rocks underlying the laboratory at Tumamoc Hill were shown on the state geologic map as Quaternary basalt. A student of the senior author has demonstrated that the so-called basalts are in fact alkali-andesites (Halva, 1961), and we now know that these alkali-andesites or doreites (Mielke, 1965) are of early Miocene age rather than Quaternary age (Bikerman and Damon, 1965). Is it any wonder then that geologists disagree on the nature and time of Basin and Range volcanism, plutonism and tec-tonism? The plain fact is that few definitive Cenozoic fossil sites were available upon which to base a chronology and geologists were forced to guess the ages of rocks in order to achieve the semblance of a time classification. We have now made considerable progress in developing a K-Ar chronology for the volcanic and plutonic rocks of the Basin and Range (Bikerman, 1965; Damon and Bikerman, 1965; Damon et al, 1964 and 1965; Mauger et al, 1965). It is the purpose of this paper to point out the main features of this chronology and to discuss the relationship of magma-tism to orogeny-epeirogeny during post-Turonian time. We will also discuss probable relationships during

Jan 1, 1967

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota's Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns' (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By C. Graeme-Barber, R. L. Bell, T. G. Langdon

An analysis is made of the formulas and ,methods used to estimate the contribution of grain boundary sliding to the overall strain of a polycrystal. The errors involved in the approximations and/or ,mistakes in earlier work are assessed quantitatively so as to make possible the critical use of previously published data. SINCE it has been found that, under conditions of very slow creep, the strain due to grain boundary sliding (?gb) may contribute as much as 80 pct of the total creep strain,1,2 it is obviously important to have reliable methods for estimating this grain boundary strain. In two recent papers Stevens3,4 has drawn attention to the pitfalls encountered in assessing ?gb. He criticizes 1) the assumptions made in the derivation of some of the formulas for ?gb, and 2) the indiscriminate averaging procedures used for obtaining the quantities substituted in these formulas. These and further criticisms of earlier work are mostly valid. Unfortunately the only formulas and procedures recommended are either impossible or very difficult to apply in practice. Furthermore no attempt is made to assess the errors involved by the earlier approximations or mistakes, and so it is not possible to make critical use of any of these early dab. The present article attempts to improve on these shortcomings by reference to empirical verification of easily applied formulas whose theoretical derivations involve some otherwise unjustifiable assumptions, and by a quantitative assessment of the errors in previous work. DEFINITIONS First it is necessary to define the terms and symbols to be used. The choice of symbols preferred here is a logical combination and extension of the v introduced by McLean5 and the u by Brunner and rant.' In Fig. 1 the two grains X and Y are displaced by the sliding vector AC. u is the component of sliding resolved along the stress axis, v is that measured perpendicular both to the stress axis and to the specimen surface, and w is that measured perpendicular to the stress axis but in the plane of the surface. Two angles define the orientation of the grain boundary: 8, between the stress axis and the surface trace of the boundary, and +, the internal angle on a longitudinal section cut perpendicular to the surface. In computing the strain resulting from the boundary displacement at all the in- dividual boundaries in a polycrystal the components u, v, or w are sometimes averaged along a longitudinal line (i.e., parallel to the stress axis), sometimes along a transverse line, and sometimes at randomly chosen boundaries. Averages obtained in these three ways are given subscripts 1, t, and r, respectively. Stevens rightly calls attention to the possibility of non-equiaxed grain shapes either at the start or at the end of deformation. In this article all values of numbers of grains per unit length will refer to measurements made before deformation. The subscripts 1 and t will be used for the number of grains per unit length obtained along longitudinal and transverse lines, r for that obtained by averaging along a number of randomly directed lines. FORMULAS FOR ?gb ?gt, as a Function of u. An obvious truth is that cgb can, in principle, be obtained by summation of all the v components at the boundaries intersected by a longitudinal line of known length I, viz.: where nl is the number of grains per unit length, parallel to the stress axis, in the unstrained specimen. There are assumptions in the analytic derivation of Eq. [I] due to Brunner and rant' but ~achinger' arrived at Eq. [la] by a rigorous method. Unfortunately the experimental procedure required by Eq. [ la] proves very difficult as boundary migration tends to obscure the points at which the longitudinal line meets the grain boundary and the errors on such measurements tend to be large, see Fig. 2. For example, on a specimen of Magnox AL 80 at a creep strain of 9.7 pct, 300 measurements of u obtained from the points of intersection of a longitudinal line with the grain boundaries gave ul = 8.95 ± 3.58 pm, or an error of ±40 pct, at the 95 pct confidence limit. These large errors due to migration may be avoided by measuring u from the separation of the segments

Jan 1, 1968