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By C. A. Mitke

(Butte Meeting, August, 1913.) 1. Character of Gases which Caused Helmets to Get Out of Order. DURING September, -1911, the fire area in the Lowell mine continually increased and gases resulting from the fire came through the upcast shaft. These gases contained such a large percentage of sulphur dioxide that the men were unable to go up and down on cages, and, within a comparatively short time, repairs in the shaft were found to be necessary. Since the fire was in sulphide ores and extended into certain timbered sections, the gases contained varying amounts of SO2 CO2, and perhaps, at times, CO. The temperature in the shaft was generally about 97°, and the relative humidity from 97 to 99.5 per cent. The corrosive action of the fumes became apparent when the cables had to be changed more often than usual, the heads of lag screws .in the guides of the shaft disappeared, and the cages needed frequent repairs. It also became necessary to repair two compartments of the shaft by putting in 150 ft. of new guides between the 600 and 800 levels and lag screws in nearly all the old guides from the surface to the 800 level. 2. Ordinary Methods of Testing Helmets which were Unsatisfactory. These conditions required all work to be done by men wearing oxygen helmets. The Draeger type was tried, and was used until all repairs were completed. At first the helmets were. tested for air circulation and air tightness and the injector was tested by water gauge according to the methods recommended by the Draeger Oxygen Apparatus Co. Six arrangements, covering .these different tests, are illustrated in the catalogue and circulars of the company.

Jan 7, 1913

By W. L. Falke, A. A. Cochran

Vast deposits of low-grade manganese ore exist in the United States, yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.1 A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the U.S. Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.2 Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4

Jan 3, 1967

Jan 1, 1934

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y' alloys by gas quenching, is extensively ordered prior to y' (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y', Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y'. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y', or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.' The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.' An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968

By D. M. Clippinger, J. J. Eidel, J. E. Frost

At Ithaca Peak, one of three peaks situated on Duval Corporation's Mineral Park property, a 'Single pulse of quartz monzonite magma intruded the isoclinally folded Precambrian Cerbat complex consisting of schist, quartzfeldspar gneiss, and amphibolite. The magma reacted with the Precambrian rocks, yielding a quartz-diorite rim. As the magma crystallized within the rim, it produced, progressing in'ward, annular bodies of quartz monzonite porphyry, quartz porphyry, and a distinctive quartz porphyry containing abundant podiform, tabular, and irregular quartz masses. These quartz masses are spatially associated with discontinuous crenulate and tabular quartz veinlets. Following crystallization, the Ithaca Peak stock and part of the surrounding Cerbat complex were fractured, producing a stockwork of predominantly northwest and northeast-trending fractures. The stockwork was then mineralized during a period of decreasing temperature by: ( 1) quartz-pyritechalcopyrite veinlets without distinct selvages and with distinct alteration envelopes in which orthoclase was altered to quartz and sericite; (2) quartz-pyrite-chalcopyrite veins and veinlets with distinct selvages and without distinct alteration envelopes; and (3) pyrite-chalcopyrite- galena-sphalerite veins. The Ithaca Peak stock was pervasively sericitized or argillized. The Mineral Park property is surrounded by a zone of propylitization Alteration and mineralization are coextensive in space and were, at least in part, coincident in time. The Mineral Park property possibly was elevated and exposed twice prior to its present exposure. The protore has been enriched by a factor of three. The Ithaca Peak supergene ore body is conformable with present topography and lies above the present water table. The shape of the ore body was controlled by erosion and oxidation of the previously enriched mineralization. Hematite, goethite, and jarosite present at the surface indicate a high primary pyrite environment, but it is possible to recognize that a small proportion of veins and veinlets contained greater amounts of chalcocite and chalcopyrite than pyrite. The igneous facies on Ithaca Peak are the products of differentiation within a solidifying rim according to Bowen's Reaction series. The innermost facies contain more quartz and orthoclase than the outer facies. Late magmatic quartz in the case of Ithaca Peak contains small amounts of pyrite and molybdenite. It is suggested that this quartz-sulfide mineralization, may also have been the product of differentiation the product of differentiation, may indicate that the later hydrothermal mineralization may also have been the product of differentiation.

Jan 1, 1968

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

By J. T. McGrath, G. B. Craig

Tensile tests on aluminum single crystals, grown from the melt, revealed that the yield stress of these crystals was raised as the amount of striation substructure was increased. The number of striation-type boundaries was varied by changing the rate of growth of the crystals. The results are interpreted in terns of a blockage of dislocation movement by striation boundaries. IMPERFECTIONS are known to have a large effect on the mechanical properties of metals. Teghtsoonian and Chalmers 1 studied a block or striation-type substructure in tin and found that the formation of the striations depended upon rate of crystal growth and orientation. They found that the angular misorienta-tion between neighboring striations varied between 15 min and 5 deg. Atwater and chalmers2 investigated striations in tin and lead, and found that purity was another factor which influenced their formation. There was a limiting purity above which the striations were straight and regular. There is little information in the literature concerning how substructures in melt-grown crystals affect strength. washburn3 introduced small-angle boundaries into zinc by a shear process and found a subsequent increase in yield stress which he attributed to the presence of these boundaries. Lauriente and pond4 found the critical resolved shear stress in aluminium crystals grown from the melt, to increase with etch pit density. The etch pits were used as an indication of growth imperfections. In Hibbard's5 work on lineage structure in copper crystals grown from the melt, he tested one crystal containing interlineage boundaries, and found a 50 pct increase in the critical resolved shear stress. Fleischer and Chalmers6, in a recent paper, mention briefly that, in the production of aluminium crystals from the melt when the growth rate was raised from 1.2 to 18 cm per hr, the yield stress increased 50 pct. They felt that the increase in yield stress with rate of growth might be attributed to a higher concentration of impurities in the gage length and also might be affected by the increased number of small-angle boundaries (striations). The present investigation was undertaken to determine the effect of the striation substructure on the strength of aluminum single crystals. EXPERIMENTAL PROCEDURE Aluminum single crystals of 99.9992 purity were grown from the melt using a technique described by Chalmers.7 The growth rate was varied from 0.6 to 20 mm per min, thus producing crystals with varying numbers of striation boundaries. To avoid prior deformation, the crystals were chemically cut to the desired length with a saturated solution of cupric chloride. They were then annealed at 580°C for 24 hr and allowed to cool slowly in the furnace. Finally, the specimens were electropolished using an electrolyte of 5 parts ethyl alcohol and 1 part perchloric acid. Each specimen was approximately 5 in. in length and 0.125 sq in. in cross section. The average orientations of the 5 series of crystals studied are shown on the stereographic projection of Fig. 1. The crystals were strained approximately 2 pct in a soft tensile machine. The strain sensitivity was 3.6 x 10-4 cm over a 5-cm gage length.

Jan 1, 1960

By E. L. Raymond

The effect of heat treatment on the microstructure and resultant notch-bar rupture life of ZNCONEL alloys X- 750 and 718 was studied. It was found that the primary effect of heat treatment in rendering these alloys notch-ductile is the elimination of any y' denuded zone adjacent to the pain boundaries. The mechanisms by which such a denuded zone can arise and be eliminated by heat treatment are discussed. InCONEL Ni-Cr alloy X-750 and INCONEL Ni-Cr alloy 718 are age-hardenable austenitic materials. Alloy X-750 is used for its corrosion and oxidation resistance and high creep-rupture strength up to 1500°F. Alloy 718 is used most effectively up to 1300°F. One of the most important areas in their development has been establishment of consistently good rupture properties, especially in the presence of a stress concentration, such as imposed by a notch. A desire to improve these properties has led to extensive studies of the effect of heat treatment on the micro structure of these alloys and their performance in stress-rupture tests. In earlier investigations"~ of INCONEL* alloy X-750, *INCONEL i s a Registered Trademark of The International Nickel Co., Inc. grain boundary carbide morphology was linked with stress-rupture properties. If, during heat treatment, the carbide MZSC was precipitated in the grain bound-ary in a cellular form, poor rupture properties re-

Jan 1, 1968

By Robert B. McCormick

THE major use for quartz crystal is in the manufacture of radio oscillator plates and telephone resonator and filter crystals. Quartz crystal is also cut and polished as a semiprecious gem stone, particularly in the colored varieties (amethyst, Brazilian topaz, and others), and often is carved into various objects of art. Prisms, wedges, lenses and other optical parts often are made of quartz crystal, usually for special- purpose instruments. Chips and small clear crystals below 100 grams in weight, called “lascas” by the trade, are the raw material for fused quartz products. HISTORICAL BACKGROUND The Greeks believed quartz to be permanently frozen water and therefore called it krustallos, which, literally translated, means clear ice; but ages before their civilization, prehistoric man had crudely cut and polished crystals for rough charms and ornaments. About 2000 B.C., the Egyptians brought the art of cutting quartz to a high level. While there are earlier examples of crystal art that have great value, working in crystal during that period became a means of artistic and religious expression that has endured through the ages. Art museums and private collections throughout the world contain many priceless pieces. They include findings from the tombs of the earliest Egyptian rulers, as well as magnificent art objects in both clear and colored crystal encrusted with silver, gold, enamel, and precious gems of oriental and European workmanship. Pierre Curie first measured the piezoelectric effect of quartz, in 188 1, by placing a weight on the surface of a quartz crystal and measuring the resulting electrical charge, which he found was proportional to the weight applied. The following year the inverse piezoelectric effect was proved by the Curies. By applying a voltage to a piece of quartz, a measurable physical displacement occurs. The first practical application of this effect was the construction of a bimorph unit to measure voltage by measuring the amount of the displacement of the end of the bimorph. The piezoelectric properties of quartz crystal remained largely a laboratory curiosity until World War I, when a supersonic device for

Jan 1, 1949

By R. G. Hawthorne

This report is concerned with fluid displacement in porous media, in those cases where viscous and gravitational forces control the displacement. Such a system would usually be found in a sand body of large physical dimensions such as an oil reservoir, although it is possible to create such a system in the laboratory. It is shown that the position of the fluid interface can be predicted by numerical calculations using a basic idea presented by Dietz. Fluid flow is considered in a vertical plane in a homogeneous, porous medium of sufficient thickness that the capillary transition zone is small in comparison with the total reservoir. A theory developed by Dietz' is used to make numerical calculations of the position of the fluid interface. The results for several conditions are compared with scaled model experiments. The results show that, for gas drive in a reservoir of steep dip, a relatively low flow rate can displace large volumes of oil before gas breakthrough. On the other hand, water injection at favorable mobility ratio and low dip may show best performance at high rates. Water tends to underride the oil and, given sufficient rime, will break through without much oil displacement. For certain conditions, which include relatively low flow rate, the interface is a straight line and its behavior is simple to calculate. At higher flow rates, the interface is unstable, and a numerical solution was programed for an automatic computer. In general, good agreement is shown between the fluid model and the computed results so long as gravitational forces have control. For a water drive at very unfavorable mobility ratio, many small water fingers appear. These viscous fingers are not controlled by the relatively small gravitational forces. When viscous fingering becomes the controlling factor, the mathematical model is oversimplified, and results do not check the fluid flow model. INTRODUCTION Present methods of reservoir analysis depend upon certain simplifying assumptions to obtain mathematical descriptions of practical use. Material-balance methods (Muskat2 or Tarner2) assume uniform fluid saturations in the entire reservoir, or in a few subdivisions of the reservoir. An unsteady-state flow calculation by West, er at considered pressure and saturation changes in flow to a well during solution gas drive, and neglected gravity effects. Results showed only a 4 per cent difference for ultimate oil recovery by the Muskat method, even though the case chosen for study was one in which unsteady-state effects should be high. The Buckley-Leverett5 method commonly assumes a one-dimensional flow system. It is applicable at high flow rates where viscous forces predominate over gravity forces. Simultaneous, parallel flow of the two fluids is assumed, and the concept of a fluid interface is not introduced. Permeabilities to each fluid for a given saturation must be known. The method is not applicable for a two-dimensional system where cross flow becomes possible. Less well known is the displacement equation derived by Dietz. This method is designed for two-dimensional flow systems and assumes a definable fluid interface within the porous medium. Dietz showed that, for a range of low flow rates, the interface would be stable. straight and at an angle of inclination which could be simply calculated. At a certain critical flow rate, the calculated interface tilt would equal the formation dip. For higher flow rates, a finger of displacing fluid would invade the displaced fluid. Dietz indicated that his method applied only to macroscopic reservoir behavior, while the Buckley-Leverett method applied to the small transition zone at the fluid interface. The examples worked out in this report are based on the fluid-displacement theory of Dietz. It is shown that the Dietz theory may be used to derive equations analogous to the Buckley-Leverett equations. In contrast to the Buckley-Leverett method, flow is considered in a plane rather than being limited to a line. Rather than a frontal advance, the movement of a fluid interface is followed. For flow rates substantially exceeding the critical rate and for high viscosity ratio, many fingers of invading fluid occur-—rather than the single finger assumed by Dietz. On the other hand, so long as some gravitational influence remains, the flow is not entirely parallel to the bedding planes as assumed by Buckley and Leverett; therefore, both methods fail to give an adequate descrip-

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

By P. Lees, N. Parkinson, K. Hartley, D. M. Donaldson

The reprocessing of advanced fuels such as carbides, oxides, and cermets, containing up to 30pct pu has been studied. Dissolution of uranium carbides in nitric acid produces appreciable quantities of mellitic acid which has undesirable effects in subsequent stages of the process. Mixed oxides containing up to about 40 pct Pu in solid solution with UO, are soluble in nitric acid and a leaching type process in nitric acid for a stainless steel/UO,. PuO, fuel containing 30 pct Pu appears to be feasible. It offers considerable economic advantages THE reprocessing of the U-Cr alloy core of the Dounreay Fast Reactor was described by Buck and others at the Second Geneva conference.' This paper described the flowsheet and plant for processing a relatively simple fuel of good dissolution charac- over total dissolution routes. A new oxidation-sub -limation process is described for metallic fuels containing up to 12 pct Mo. New data is presented on the solvent extraction of uranium and plutonium nitrates into tributyl phosphate -odorless kerosene and of the influence of radiolytically produced acid phosphates on this part of the process. It is concluded that there are no insuperable difficulties which will prevent the satisfactory reprocessing of high burn-up plutonium fuels by a solvent extraction route. teristics and of low-plutonium content after irradiation. However, it has been clear for some time that more satisfactory operation of the reactor can be obtained by the use of a core with better irradiation performance than U-Cr alloy and a U-Mo alloy will be used for the next charge. Recent modifications to the core mean that it is now possible to carry out irradiations of fuel element subassemblies similar to those which might be used in a fast power reactor and trials with plutonium-bearing fuel elements will be made in the relatively near future. These changes have meant that a considerable amount of reprocessing development work has had to be carried out for

Jan 1, 1963

By L. T. Larson, P. M. Basinski

In the northern Reese River Valley uranium is corroded with Middle Pliocene zeolites. These zeolites were diagenetically derived from rhyolitic volcanic glass deposited in a saline- alkaline lake. X-ray diffraction, scanning electron microscopy, and chemical studies reveal clinoptilolite, analcime, and enonite to be pesent and that these minerals can concentrate at least 0.7% uranium from solution. Most anomalous drill cuttings contain zeolite and zeolites are believed to host the uranium. Research suggests the uranium mineralization is conceptually analogous to the Tono mine, Japan.

Jan 1, 1981

Jan 1, 1912

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

President and Director GROVER J HOLT, '59, Ishpeming, Michigan Past President and Director CARL E REISTLE, JR, '58, Houston, Texas President-elect and Director AUGUSTUS B KINZEL '60, New York City Vice-Presidents and Directors W A DEAN, '58, Cleveland Ohio W W MEIN, JR, '58, San Francisco, Calif L E ELKINS, '59, Tulsa, Okla J L GILLSON,'59, Wilmington, Delaware E C BABSON, '60, Calgary, Alberta, Canada R V PIERCE, '60, Salt Lake City, Utah

Jan 1, 1957

By A. J. Brown

The causes that have formed fissures in the earth's crust, and the agencies that have converted them into metallic beds, are amongst the most important and interesting subjects that can engage the attention of the mining engineer or the scientist. They lie at the very base of the whole system of vein geology, and until something like a correct theory can be arrived at with regard to them, the science as such is necessarily very incomplete. he data for such a theory, owing to a lack of careful and systematic observations in countries pre-eminently metalliferous, like Mexico and the States of Central and South America, are almost entirely wanting. Doubtless there has been abundant speculation on the subject, from the earliest times down to the present, in every country where mining has been one of the leading industries of the inhabitants. Perhaps the theory of Elie de Beaumont more nearly approaches a satisfactory explanation than that of any contemporary authority. The most recent investigations, both in Europe and on this continent, tend to produce the conviction that the phenomena of metallic fissure lodes are in some way connected with, and dependent upon, plutonic agencies— not, however, as the direct product of volcanic activity, but rather as the result of chemical agencies called into play through its aid. Active volcanoes generally produce only the well-known types of volcanic rocks, though, perhaps, well-marked cases can be shown where these contain ores of copper, etc., evidently derived from the same deepseated source as their hypogene gangue. To prove that there is a connection between metallic lodes and plutonic rocks, it is not necessary that the ores should in all cases occupy fissures within the limits of masses of propylite, rhyolite, or other like rocks, or be

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

A simple and inexpensive mercury-tracer method has been develohed to study rates and Patterns of gas flow in blast furnaces. A Pulse of mercury is injected into the hot blast, and its arrival at the sampling Point is recorded by an electronic circuit that measures resonant absorbtion of ultraviolet light by mercury vapor in the gas aspirated .through the detecting. cell. A rapidly developing interest in blast-furnace technology in recent years has created a strong demand for precise knowledge of the rates and patterns of gas movement through the stock column. Classical fluid-flow theory cannot supply the desired information because the complexity of the blast-furnace situation precludes the accurate determination of many of the parameters required for solution of the equations. In fact some of the terms employed in fluid-flow treatments become almost meaningless under blast-furnace conditions. The void fraction of the stock column, for example, varies widely from place to place and is affected by the segregation of charge materials, attrition of lumps during descent, and channeling. Gas density varies with changes in local pressure, temperature, and composition, while viscosity varies with temperature and composition. Even if mean values for these functions were acceptable, they would be either impossible or extremely difficult to determine with a high degree of accuracy since the value of the mean for all gas properties would depend upon the flow distribution itself. Attempts to study gas movement by the pitot-tube determination of kinetic pressures have met with little acceptance. Reproducibility of results is extremely difficult to achieve in a situation where alignment of the tube orifice with respect to the flow direction in tortuous channels cannot be guaranteed. Because of these difficulties it would appear that progress can be achieved only with a direct method of measuring gas velocities and determining the shape of flow paths through the stock. The establishment of such a method is described in this paper. SELECTION OF METHOD Direct measurement suggests the use of a tracer by means of which the progress of a "parcel" of gas can be followed through the furnace. Several requirements must be met before any selected material can be considered a suitable tracer. First of all, it must be a substance not normally present in blastfurnace gas or dust; otherwise its presence in a gas sample will have little significance. It should be volatile at temperatures normally existing within the furnace, to ensure that it will travel with the gas, as a gas. It should possess special properties enabling its presence in the gas to be detected readily, and it should not undergo exchange reactions with any material normally present within the furnace, including refractories and coke as well as all components of the metal and slag. Radioactive materials naturally are considered because their radioactivity renders them susceptible to detection. However, of the many radioactive materials available, almost all are eliminated from final consideration by their unsuitability in terms of other properties. Radioactive silicon, carbon, calcium, phosphorus, and many others have been considered and discarded, either because they are not volatile over the whole range of significant temperatures, or because they could be expected to undergo exchange reactions with burden or refractory materials. Others which might be suitable in terms of these properties are eliminated because of a low activity, short half life, or the necessity for fragile counting apparatus. Of the many elements available in radioactive form, perhaps radon is the only one suitable for blast-furnace gas-flow studies. This has been used in several investigations1-4 with considerable success. The use of radiotracers has certain inherent disadvantages. One is the cost. An appreciable sum must be allowed for materials each time a test is made. Also, special methods of handling must be employed, and very often the progress of an investigation must be governed by the availability of isotopes and the delivery arrangements that can be made for them. An advantage is immediately gained if the tracer material can be a substance which can

Jan 1, 1960