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INSTITUTE OF METALS DIVISION Ferrous and Nonferrous Physical Metallurgy (By-laws in Transactions, Vol 156, 1944) Established as a Division April 26, 1918 Walter A Dean, Chairman R. M. Brick, Past-Chairman Morris Cohen, Senior Vice-Chairman J H Scaff, Vice-Chairman Ernest Kirkendall, Secretary-Treasurer

Jan 1, 1952

By Lucien Eaton

VENTILATION in the iron mines of the Lake Superior region in nearly all cases is natural; that is, it is induced by the difference in elevation between different outlets in the mine and by the difference in temperature of the air in the mine and that outside. This difference in temperature is frequently augmented by placing a steampipe in the upcast shaft; but aside from this, artificial aids to ventilation have been rare until - recent years. In some of the older mines, as at the Cliffs Shaft mine at Ishpeming, Mich., in the 80's, fans have been used when there was only one opening to surface, but their use was abandoned as soon as a natural circulation of air started. In recent years, the Newport mine at Ironwood, Mich., was the first to use positive mechanical ventilation. The installation was not large enough, however, to give definite results, reliance being placed largely on natural ventilation. With the coming of warm weather in the spring of 1914, the necessity of positive mechanical ventilation at the Lake mine of the Cleveland-Cliffs Iron Co. at Ishpeming, Mich., became evident. The workings of the Lake mine are under the bed of old Lake Angeline, which was pumped out in 1894, and the mine had been in operation for 6 years prior to that date making a total of 26 years of continuous operation. The total production, up to 1914, amounted to over 8,000,000 tons. The ore was first mined by square-set rooms and pillars, but this was later changed to top slicing and caving. Both methods required the use of large amounts of timber, probably 80,000,000 board feet in all, practically all of which remained in the timber mat. The slow oxidation of this timber was one of the principal causes leading to the installation of mechanical ventilation. The mine was served by only one working shaft, called No. 4, a second outlet being provided by a raise to the surface from the old workings on the south side of the mine. This raise was the "down cast;" but it was very small and the drifts and raises leading to it were too small and crooked to permit an adequate amount of air to enter the mine, especially during the warmer weather. Measure-

Jan 8, 1920

ALEXANDER, JOHN S, M,'74-6,'81-3 ASHBURNER, C A, M, '85-7 ASMUS, GEORGE, Dl, '78-80 BACON, D H , M, '00-2 BAYLES, JAMES C , M,'80-2,'91-3 P, '84-5, V,'88-9 BIRKINBINE, JOHN, M, '83-5, V, 'S7-J, P, '91-2 BLAIR, THOMAS S , M, '74-43 BLAKE, WILLIAM P , V,'71-4,'76-7,'05-6 BLANDY, JOHN F, V,'71-3,'78-9 BLOW, A A, C, '05-7 BOWIE, A J , JR, V,'93-4 BRAMWELL, J H , A1, '89-91 BROOKS, THOS B , M, '72 BRUNTON, D W , V, 97-8 BUCK, STUART M , M, '83-5 BURDEN, JAMES A, V,'80-1 BURNHAM, WILLIAM, M, '82-4. CAMPBELL, H H, M, '93-5 CHAMBERLAIN, H S , V, '96-7 CHANNING, J PARKE, V,'08 CHRISTY, S B , V. '91-2, '07-8 CHURCH, JOHN A, M, '79-8l,'94-6, V, '07-8 COGSWELL, W B, V, '74-5,'86-7

Jan 1, 1910

ALEXANDER, JOHN S, M,'74-6,'81-3 *ASHBURNER, C A, M, '85-7 ASMUS, GEORGE, Dl, '78-80 BACON, D H , M, '00-2 BAYLES, JAMES C , M,'80-2,'91-3 P, '84-5, V,'88-9 BIRKINBINE, JOHN, M, '83-5, V, 'S7-J, P, '91-2 BLAIR, THOMAS S , M, '74-43 BLAKE, WILLIAM P , V,'71-4,'76-7,'05-6 *BLANDY, JOHN F, V,'71-3,'78-9 BLOW, A A, C, '05-7 BOWIE, A J , JR, V,'93-4 *BRAMWELL, J H , A1, '89-91 BROOKS, THOS B , M, '72 BRUNTON, D W , V, 97-8 BUCK, STUART M , M, '83-5 *BURDEN, JAMES A, V,'80-1 BURNHAM, WILLIAM, M, '82-4. CAMPBELL, H H, M, '93-5 CHAMBERLAIN, H S , V, '96-7 CHANNING, J PARKE, V,'08 CHRISTY, S B , V. '91-2, '07-8 CHURCH, JOHN A, M, '79-8l,'94-6, V, '07-8 COGSWELL, W B, V, '74-5,'86-7

Jan 1, 1910

By F. G. Clapp

IT is to be hoped that no casual reader will erroneously refer to the latest publication' of the Division of Public Relations of the American Petroleum Institute, as being "Petroleum Facts and Fancies." The facts are so faithfully derived and the figures are so authentically sponsored by the highest sources that no person can read this valuable volume (287 pages and numerous tables) without being convinced that every- thing therein set forth is "the truth and nothing but the truth." Yet, having read the volume from the perspective of the world's petroleum industry and with a critical attitude that comes from years of study of the subjects discussed, I find myself tempted to cogitate and to envisage a few of the fancies that come to mind as a fitting sequel.

Jan 1, 1929

By E. M. Murphy

Eight years ago the Hecla mine, a lead-silver producer, situated at Burke, Idaho, was producing ore from but two levels, the 300- and the 600-ft. All hoisting was done with a 12- by 16-in. slide-valve, double-reel, hoist. The hoist was being worked to its capacity and was unsuitable for hoisting from greater depths. As the work of opening a new level was about to be started, it became necessary to remodel the then-existing equipment or install a new hoist. The recent advent of electricity from Spokane had made available a cheaper power than steam. By a series of tests conducted throughout the Cæaur d'A1ene district, it was found that it cost $109 per year to generate a horse-power with steam. Electric power was to be had for $50 a horse-power per year. It was decided to substitute for the engines a motor-drive, of sufficient capacity to operate from the 900-ft. level, and ultimately install an entirely new hoist. After disconnecting the engines, installing a new shaft, and making a few minor changes, a 300-h-p., 2,300-volt, 514-rev. per min., variable-speed motor of the induction type was geared to the reel-shaft. The reels were supplied with 3/8- by 4-in. flat rope, and the duty of the hoist was about as follows: Cage, 1,700; ore, 2,600; car, 1,400; rope, 2,250; total, 7,950 pounds. The Bristol ammeter chart, Fig. 1, shows the combined current-consumption of the hoist- and mine-motors. The large intermittent load is clearly shown; this produced harmful fluctuations in the voltage of the long, lightly-loaded, 60,000-volt transmission-line from Spokane to the Cæmur d'A1enes. The power company received no compensation for the increased cost of producing power for this intermittent or fluctuating load. In order to protect its system from similar excessive

Jan 1, 1913

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

By A. M. Rowe, I. H. Silberberg

A computer program was written to predict the phase behavior generated by the enriched-gas-drive process. This program is based, in part, on a new concept of convergence pressme, which is then used to select vapor - liquid equilibrium ratios (K-factors) for performing a series of flash calculations. The results of these calculations are the equilibrium vapor and liquid phase compositions which define the phase envelopes. The program was used to predict phase envelopes for 11 different hydrocarbon systems on which published experimental data were available. The predicted and experimental results compare favorably. INTRODUCTION The reservoir engineer is frequently faced with the problem of predicting what will happen if gas is injected into a reservoir. One aspect of this, general problem is predicting the phase changes that will occur when a non-equilibrium gas displaces a reservoir fluid. In particular, a "dry" gas, upon displacing a volatile oil, will pick up intermediate components from the oil. On the other hand, a "wet" gas, containing a high concentration of intermediates, will lose some of these components to a relatively low-gravity, non-eouilibrium1- crude. It is this latter Drocess. occurring in the enriched-gas displacement, which is treated in this paper. In the past, these phase changes have been determined experimentally and the results incorporated into various modifications of the Buckley-Leverett analysis.112 Such experimental work is time consuming, and the results are sensitive to numerous experimental errors. With the wide availability of high-speed digital computing equipment and numerous correlations pertaining to the vapor-liquid equilibria of hydrocarbon systems, it is now practical to calculate such phase behavior. This paper describes a computer program for performing these calculations. THE ENRICHED GAS DISPLACEMENT PROCESS Experimental results have shown that oil recovery can be significantly increased by enriching the displacing gas with intermediate hydrocarbon c0m~onents.3 The essential features of the phase behavior generated by this enriched-gas-drive process are commonly illustrated with ternary diagrams such as Fig. 1.4 In this figure, Gas D, which contains a high concentration of intermediate hydrocarbons with respect to the undersaturated Crude A, is injected into the reservoir. When D contacts A, gas goes into solution until the oil becomes saturated (Point. B). Further contacting of Gas D and saturated Oil B results in a Mixture C which separates into Vapor Y(c) and Liquid X(c). Liquid X(c) is contacted by additional Gas O, resulting in Mixture E which separates into Vapor Y(e) and Liquid X(e). Repeated contacts of the liquid by the injected gas will eventually result in Liquid X(4 of maximum enrichment existing in equilibrium with Gas Y(d). The equilibrium tie-line X(4 Y(4, when extended, passes through the Point D representing the enriched injection gas. For systems of more than three components, the predicted equilibrium states are dependent upon not only reservoir temperature and pressure, but also the compositions of the crude oil and injected gas. If the gas is sufficiently enriched, a miscible displacement is generated. Line If is tangent to the phas,e envelope at the critical point (Point Z) and represents the limiting slope of the tie-lines as the critical state is approached. Point 1 therefore represents the minimum enrichment of injection gas required to generate a miscible displacement. Point G represents the minimum enrichment required for initial miscibility of the injection gas with Crude A. Accra has presented a method to be used for prediction of oil recovery by the enriched gas displacement process.l To develop the phase behavior data needed, he designed the experimental procedure described in the following quotation from his paper: The original liquid was contacted by a volume of displacing gas and allowed to come to equi-

Jan 1, 1966

By M. van Swaay, C. E. Birchenall

Palladium has a large capacity for the dissolution or occlusion of hydrogen; the gas also diffuses very rapidly through the metal. Palladium thimbles are widely used in the laboratory for purification of hydrogen by diffusion. The use of palladium filters could be extended to several large-scale applications if greater stability of the permeation process could be attained. In this paper a number of aspects contributing toward this goal are discussed, and new data on solubility and diffusivity are given. Palladium sheets of 0.005, 0.010, or 0.020 in. thickness were prepared by three procedures: casting and rolling, sintering palladium powder, and sintering palladium powder to which 0.1 pct thorium oxide had been added. Half-inch diam circular specimens were cut and clamped in a stainless steel holder provided with knife edges to seal the palladium sheet with soft copper gaskets. The seals were tested for leaks at l0-5 mm Hg. No difficulties from this source were encountered even after many temperature cycles in the system. The holder was silver-soldered to Kovar-glass seals and attached to the system through glass ball joints. Each joint was sealed with Apiezon wax and was adjacent to a cold trap. In several experiments the holders were fused directly into the system, eliminating the ball joints, to show that the wax did not affect the filter. Three filter holders were supported in holes in a stainless steel cylinder, which also acted as a temperature equalizing block inside the resistance wound furnace. The measuring thermocouple was inserted in one of the holders. A potentiometric controller with control thermocouple on the furnace heater winding maintained ± 0.2oC. Electrolytic hydrogen was purified and stored as shown in the flow diagram, Fig. 1. It could be admitted to either or both sides of the palladium specimens. Only a mechanical pump was used, for even high pumping speeds would not bring the pressure on the off-gas side of the filter below 10 to 50p Hg owing to the rapid hydrogen flow through the filters. A series of steady-state permeability studies allowed identification of several conditions of permeability loss. A constant fore pressure was maintained while the low-pressure face was pumped. After enough time had elapsed for a steady flow to be established the pump was cut off, and the rate of pressure increase in a thermostated bulb was measured to determine the flow rate. The time delay method of Daynes1,9 was adopted since it offered the possibility of determining solubilities and diffusivities. For each measurement both sides of the filter were evacuated for 15 min, which gave about 10-4mm Hg residual pressure. Hydrogen was admitted to one side or the other of the filter at a fixed pressure. The pressure on the off-gas side was observed as a function of time. A

Jan 1, 1961

By W. Rostoker, H. Nichols

It has been demonstrated in previous work1'2 that wetting of aluminum alloys by liquid mercury can cause fracture to occur with substantial suppression of prior plastic flow. This has been interpreted as the action of a critical liquid species in reducing the cohesive strength of a stressed solid at sites of potential crack nucleation. In this way the critical transverse stress for fracture nucleation is reached at much lower stresses than is normally the case. The stresses for both fracture nucleation and fracture propagation are depressed by the same mechanism. In so doing the plastic-energy component of fracture energy is reduced to a level which is of the same order of magnitude as the surface, interfacial, or cleavage energy. Recent work2 has illustrated the influence of dispersed precipitates, cold work, and combinations of these on brittle fracture associated with plastic strains of the microyield order of magnitude. This has been rationalized in terms of the contribution of internal microstress fields to the stress magnifications at points of obstruction of active slip bands in a stressed metal. The presently reported studies on an Al-4-1/2 pct Mg alloy amplify this subject by introducing thermal-mechanical conditions which can produce strain aging. As amply demonstrated by Phillips, Swain, and borall, the tensile behavior of aluminum alloys containing magnesium reveals a yield-point elongation and successive discontinuous elongations over the whole plastic-strain range. This gives a stepped or serrated character to the stress-strain diagram. The yield-point elongation is not temperature-dependent. On the other hand, the discontinuous extensions in the plastic-strain range are gradually suppressed by lower temperatures of testing. At -78"C, only the yield-point elongation persists. The yield-point elongation itself can be suppressed by rapid quenching to room temperature from an annealing temperature of 500°C. The argument presented by Phillips et 1. and Cottre114 is that the yield-point elongation derives from surmounting at a critical stress the restraint to slip by grain boundaries which have been reinforced by appreciable magnesium-atom segregation. The serrated character of the plastic-strain range is the result of rapid strain aging during the test. This is made possible by the inevitable proximity of magnesium atoms to any dislocation line. In the Al-4-1/2 pct Mg alloy there is one magnesium atom for every twenty-two aluminum atoms and, with a coordination number of 12, a magnesium atom is on the average only about two atomic distances from any given lattice site. Rapid strain aging is therefore a reasonable expectation. A study of mercury embrittlement of the Al-4-1/2 pct Mg alloy (commercial designation 5083) provides an opportunity to relate the interplay of grain size, grain boundary restraint to slip and strain aging in the brittle-fracture process. One lot of commercial sheet material of 0.125-in. thickness was used for all of the tests. The specimen shape and test procedures used were the same as those described in a previous publication.2 A range of grain sizes between 0.0057 and 0.0125 mm was produced by various combinations of plastic prestrain and annealing. The coarsest grain was somewhat elongated in shape. In this case the measurement was taken in the direction transverse to the axis of tension as more meaningful to a brittle-fracture process. In the annealed condition, specimens wetted with mercury failed with zero permanent elongation at stresses slightly below the normal yield point, i.e., stresses at 0.05 to 0.2 pct strain. Since this occurs before yield-point elongation can begin, fracture derives from slip contained within individual grains and restrained from propagating across grain boundaries. No significant difference in wetted fracture stress was observed between specimens which had been water-quenched or furnace-cooled from the annealing temperatures. This signifies that the degree of magnesium segregation at grain boundaries

Jan 1, 1964

By P. W. Bakarian, John C. McDonald

Three magnesium alloys were processed in various ways to exhibit a wide variation in the ratios of yield strength and tensile strength in the rolling direction compared to the cross-rolling direction. Basal-plane pole figures were prepared from several specimens. A fair correlation was observed between the property ratios and the ratio of percent of poles oriented in the cross-direction quadrants compared to the percent oriented in the rolling-direction quadrants of the pole figures. THE modes by which magnesium crystals deform are such as to lead to marked preferred orientations in all forms of wrought products. The effect of the active modes at room temperature, coupled with these orientations, is often to produce a lower compressive yield stress compared to the tensile yield stress. The phenomenon is due to easy twinning in compression, and has been well-related to the preferred orientations as described by basal-plane pole figures of the hcp magnesium single crystal. The literature contains some information on the variation with test direction of the tensile properties of sheet, but no quantitative relationship to the observed pole figures has been established. These effects have been reviewed in the few com- prehensive treatises in English which have been written on magnesium technology and metallurgy.1°3 Roberts presents several pole figures, but no tensile-property data in the plane of the sheet. Raynor has no pole figures, but quotes Frommer's4 results. The information in Beck's compendium more or less parallels the results of Jones and powell.5 In both a Mg + 1.5 Mn alloy and a Mg + 4.6 A1 alloy, cold rolling was found not to change the general situation of higher properties in the cross-rolling direction,* than in the rolling direction. Thomas'6 X-ray studies of Jones and Powell's specimens did not permit correlation of properties and preferred orientation. Ansel and Betterton7 report tensile and compressive properties on three other alloys as a function of degree of cold rolling, plus a recrystallizing anneal. As rolled, there was a change in anisotropy with degree of reduction, but all alloys were reasonably isotropic in tension when annealed. X-ray diffraction photograms illustrated the kinds of orientations present, but were not correlated with the properties. Bakarian8 has described a method of determining quantitatively a preferred orientation, and illustrated the method by applying it to pure magnesium and two of its alloys. This method was used in the present work as a basis for correlating the strength properties with the texture.

Jan 1, 1965

By R. P. Marshall

This note describes positive evidence that hydrogen in titanium alloys diffuses under the influence of a thermal gradient. The experiments confirmed the expected similarity of this system to the H-Zr system and produced qualitative information on the magnitude of the heat of transport for hydrogen in titanium alloys. This effect has practical importance in applications where titanium alloys operate in a thermal gradient under conditions such that hydrogen embrittlement may develop within the expected lifetime of the structure, for example in supersonic aircraft service. The theories of thermal-gradient diffusion may be found in recent reviews and experimentation in this field by Shewmon,1 Sawatzky,2 Markowitz,3 and Darken and Oriani.4 The basis for Soret thermal diffusion is the "heat of transport", denoted by Q*. This is an energy term for the amount of heat (energy) transferred by atomic diffusion, and can be either positive or negative signifying a driving force for atomic diffusion to the cooler or hotter region, respectively. Experimentally, Q* is determined by plotting the natural logarithm of the point-to-point concentrations after exposure to a thermal gradient vs the respective point-to-point temperatures in units of the inverse absolute temperature scale. The slope of the straight line is Q*/R, R being the gas constant. For the titanium experiments, specimens (3 by 1 by 1/16 in.) of a) commercially pure titanium, b) the 8 Al-1 Mo-1 V titanium alloy, and c) the 6 A1-4 V titanium alloy were exposed to thermal gradients of 6° to 115°C per in. for 18 days at 250° to 550°C. The temperature gradient was in the direction of the 3-in. dimension. The hydrogen concentrations existing after exposure were determined on sections of the specimens by vacuum extraction. Three sections of unexposed sheet of each alloy were analyzed as standards to allow a check for hydrogen

Jan 1, 1965

By C. A. WARNER

AN OIL and gas mining lease contract, as entered A into by and between 'the lessor and the lessee, contains certain express covenants stipulating, in part at least, the exact performance thereof; it also contains certain implied covenants, among which may be included that of protection of the leased premises against drainage by the drilling of necessary offset wells. In the drilling for, and production of, oil and gas, however, it not infrequently happens that the lessee, acting in good faith, does not deem it prudent to, drill a test thereon even though the location for such test is offset by a producing well on an adjoining lease. Such conclusion, on the part of the lessee, is generally construed by the lessor as constituting a breach of the implied covenant mentioned above, and he may take proper action to secure satisfaction therefor. The action against the lessee is generally for cancellation or relinquishment of the lease, together with, or apart from, claims for damages allegedly sustained through failure to properly protect against drainage of the leased premises.

Jan 1, 1931

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By K. H. Coats

This paper presents the development and solution of a mathematical model for aquifer water movement about bottom-water-drive reservoirs. Pressure gradients in the vertical direction due to router flow are taken into account. A vertical permeability equal to a fraction of the horizontal permeability is also included in the model. The solution is given in the form of a dimensionless pressure-drop quantity tabulated as a function of dimensionless time. This quantity can be used in given equations to compute reservoir pressure from a known water-influx rate, to predict water-influx rate (or cumulative amount) from a reservoir-pressure schedule or to predict gas reservoir pressure and pore-volume performance from a given gas-in-place schedule. The model is applied in example problems to gas-storage reservoirs, and the difference between reservoir performances predicted by the thick sand model of this paper and the horizontal, radial-flow model is shown to be appreciable. INTRODUCTION The calculation of aquifer water movement into or out of oil and gas reservoirs situated on aquifers is important in pressure maintenance studies, material-balance and well-flooding calculations. In gas storage operations, a knowledge of the water movemenr is especially important in predicting pressure and pore-volume behavior. Throughout this paper the term "pore volume" denotes volume occupied by the reservoir fluid, while the term "flow model" refers to the idealized or mathematical representation of water flow in the reservoir-aquifer system. The prediction of water movement requires selection of a flow model for the reservoir-aquifer system. A physically reasonable flow model treated in detail to date is the radial-flow model considered by van Everdingen and Hurst.1 In many cases the reservoir is situated on top of the aquifer with a continuous horizontal interface between reservoir fluid and aquifer water and with a significant depth of aquifer underlying the reservoir. In these cases, bottom-water drive will occur, and a three-dimensional model accounting for the pressure gradient and water flow in the vertical direction should be employed. This paper treats such a model in detail — from the description of the model through formulation of the governing partial differential equation to solution of the equation and preparation of tables giving dimensionless pressure drop as a function of dimensionless time. The model rigorously accounts for the practical case of a vertical permeability equal to some fraction of the horizontal permeability. The pressure-drop values can be used in given equations to predict reservoir pressure from a known water-influx rate or to predict water-influx rate (or cumulative amount) when the reservoir pressure is known. The inclusion of gravity in this analysis is actually trivial since gravity has virtually no efFect on the flow of a homogeneous, slightly compressible fluid in a fixed-boundary system subject to the boundary conditions imposed in this study. Thus, if the acceleration of gravity is set equal to zero in the following equations, the final result is unchanged. The pressure distribution is altered by inclusion of gravity in the analysis, but only by the time-constant hydrostatic head. The equations developed are applied in an example case study to predict the pressure and pore-volume behavior of a gas storage reservoir. The prediction of reservoir performance based on the bottom-water-drive model is shown to differ significantly from that based on van Everdingen and Hurst's horizontal-flow model. DESCRIPTION OF FLOW MODEL The edge-water-drive flow model treated by van Everdingen and Hurst1 is shown in Fig. la. The aquifer thickness b is small in relation to reservoir radius rb. water invades or recedes from the field at the latter's edges, and only horizontal radial flow is considered as shown in Fig. 1b. The bottom-water-drive reservoir-aquifer system treated herein is sketched in Fig. 2a and 2b. Here the aquifer

By John Wulff, Richard P. Seelig

THE importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by sub- sequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be con- trolled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper. In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshin1 on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin1 and Rakovski.2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,1 based on a hydro- dynamic analogy, however, leads to but another way of plotting density and pres- sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. DENSITY GRADIENTS IN COMPACTS The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By DR. RICHARD RATHBUN

(Washington Meeting, May, 1965.) THE remarks of Dr. Rathbun in his address of welcome render it unnecessary that I dwell either upon the history or aims of the National Museum, and enable me to proceed at once with a brief descriptive outline of the Department for which I am responsible, and this with particular reference to that division devoted to applied geology. The amount of geological material brought together prior to 1876, under the various Congressional acts quoted, was, though valuable, comparatively small. It consisted mainly of the collections made by Professor J. D. Dana and his assistants during the Wilkes Exploring Expedition; by the various geologists accompanying the surveys of the Pacific railroads in 1854-55; the Surveys West of the 100th Meridian under the direction of the Engineering Corps of the Army; the United States geological surveys under direction of Dr. F. V. Hayden ; and the various Land Office surveys. Prior to 1873 there were no paid assistants to care for these collections. They were studied, if studied at all, by " collabrators," so-called, several of whom had offices and even sleeping apartments in the Smithsonian Institution. In the list of these collaborators are found such names as Conrad, Cope, Gabb, Leidy, Lesquereux, Meek, and Newberry. The building now occupied by the National Museum was designed primarily to make room for the great mass of material secured in 1876 at the close of the Centennial Exposition in Philadelphia. As completed in 1880, it afforded opportunity for expansion and incidental organization on much more practical basis than had previously existed. This found expression in the creation of numerous departments with salaried officials to take charge of the various collections. With the appointment of Dr. George W. Hawes to the position of Curator of Geology and Mineralogy, in 1881, and Dr.

Jul 1, 1905

CONTENTS PAGE MERRISS, M. H.-Direct Electrolysis of Black-copper Anodes of High Nickel-lead Content. Discussed by C. S. Witherell, C. P. Linville, G. E. Dalbey, M. H. Merriss 1 GRISWOLD, GEORGE G.-Calculating the Zinc for Desilverizing Lead Bullion by the Parkes Process. Discussed by C. S. Witherell, George G. Griswold, Milo W. Krejci, Lawrence Addicks, W. F. Gross, H. H. Alexander, A. F. Beasley, C. P. Linville 3 ALEXANDER, H. H. and STACK, J. R.-The Reduction and Refining of Tin in the United States. Discussed by Edward F. Kern, J. R.' Stack, R. L. Hallett, C. R. Hayward, William H. Bassett, R. C. Canby, H. G. S. Anderson 20 GREENAWALT, WILLIAM E.-Greenawalt Electrolytic Copper Extraction Process. Discussed by Stuart Croasdale, Colin G. Fink, Arthur L. Walker, Edward F. Kern, Henry A. Tobelmann, Oliver C. Ralston 26 BENEDICT, C. H. and KENNY, H. C.-Ammonia Leaching of Calumet and Hecla Tailings. Discussed by G. E. Dalbey, C. H. Benedict 34 RALSTON, OLIVER C.-Hydrometallurgy of Lead. Discussed by F. L. Bosqui, Jr., George D. Van Arsdale 34 TAINTON, U. C. and LEYSON, L. T.-Electrolytic Zinc from Complex Ores. Dis¬cussed by W. G. Woolf, C. A. Hansen 39 Direct Electrolysis of Black-copper Anodes of High Nickel-lead Content Discussion of the paper of M. H. MERRISS, presented; at the New York Meeting; February, 1924, and, issued, as Paper No. 1273-M, with MINING AND METALLURGY, September, 1923. C. S. WITHERELL, New- York, N. Y. (written discussion).-This paper is particularly valuable in that it gives the results of operations -carried out under conditions differing from standard practice. In the electrolytic refining of copper, as in other kinds of metal refining, it is occasionally necessary to treat extraordinary foul or complex material, in which cases 'it is valuable to know what other metallurgists have accomplished under similar conditions. As tapping the slimes-covered anodes brought the tank-voltage down to 0.45 to 0.50 volt, the counter electromotive force was, probably not more than 0.1 or 0.2 volt; hence the so-called polarization was, mainly,

Jan 6, 1924