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By H. O. Hofman

PAGE I. Introductory,.......... 258 11. Condensed Account of Past and Present Plants,. .. 259 111. The Ores. Table I., Average Analyses,..... IV. Metallurgical Treatment—Roasting OF Ores,... The Allen-O'Hara Furnace,....... The Wethey Furnace,........272 The Pearee Turret-Furnaces,....... 273 The MacDougall Furnace,.......275 Original MacDougall,.......276 Herreshoff,......... Evans-Klepetko,........ General Results (Table II.),.......282 V. Smelting Ores in The Blast-Furnace,...,. Table 111. Examples of Montana Blast-Furnace Smelting,. 284 Table IV. Analyses of Coke and Coke-Ash,. .. . VI. Smelting Ores in the ReveRberatory Matting-Furnace,. 289 Table V. Percentage of Components of Charge,. .. 290 Table VI. Analyses of Flue-Dust and Briquettes,. .. Table VII. Examples of Montana Reverberatory-Smelting,. 292 Table VIII. Analyses of Coals,...... Table IX. Analyses of Producer-Coal and Ash,. .. Details of Practice,........297 VII. Converting Coppr-Matte,....... 302 Table X. Analyses of Materials of Converter-Linings,. . 306 Table XI. Montana Converters,......308 Yield of Metal..........308 VIII. Electrolytic Refining of Copper,..... Refining of Cathodes,........ 313 Table XII. Details of Electrolytic Refineries,. .. . Table XIII. Efficiency of Some Rocky Mountain Coals,. . 316 I. Introductory. In 1901,* this country produced 268,782 long tons of fine copper. Of this total, Montana is credited with 102,621 long tons, or 38.2 per cent.

Jan 1, 1904

By H. R. Hanley

THE characteristics of alloyed anodes and their influence on the products of electrolysis and power consumption have been noted previously in the literature.1 This paper presents data in continuation of the subject given in an earlier paper by the authors.2 As noted in the authors' previous paper, the objectives of this work are the reduction in the cell voltage and the purity of the cathode product resulting from the use of alloyed lead anodes. The fundamental facts developed in the previous paper were: (1) that the presence of a small amount of calcium lowers the anode potential approximately 50 per cent. below that of pure lead; and (2) that thallium when present to the extent of 4 per cent. rendered the anode practically stable, thereby lowering the contamination of the cathode by lead to a very insignificant amount. The specific features determined in this recent work are as follows: 1. The lowest limit of calcium in the lead which will still give maximum lowering of the anode potential. 2. The characteristics of the thallium-calcium-lead anode. 3. The characteristics of the silver-calcium-lead anode. 4. The characteristics of the thallium-silver-calcium-lead anode. It was determined that 0.1 per cent. calcium in the anode was sufficient to lower the anode potential approximately 50 per cent. Table 1 shows the characteristics of alloyed anodes tested. The anode composed of 0.1 per cent. calcium, 4 per cent. thallium, and 95.9 per cent.

Jan 1, 1931

1. How Does One Determine Whether an Ore Body Will Block-cave? Page Mark A. Smith......... 122 Harry A. Leidich........ 122 McHenry Mosier ...,.. 22 R. W. Hughes ........ 122 Sherman R. Burdick ....... 123 R. T. Gallagher........I 23 Benjamin F. Tillson...... 123 Lucien Eaton...........123 C. F. Jackson..... . .. 123 Philip B. Bucky........... 126 2. How Does One Determine the Block Dimensions and the Development Work Necessary to Make an Ore Body Cave? Mark A. Smith... 125, 127, 129 Harry A. Leidich..........126 McHenry Mosier......126, 127, 132 R. W. Hughes...........126 Sherman R. Burdick.........127 R. T. Gallagher...........127 Benjamin F. Tillson......127,131 L. E. Young............127 Robert D. Hoffman.......128, 132 Gerald Sherman..........128 Philip B. Bucky......130, 131, 132 K. S. McClellan..........132 Tell Ertl.............132 3. How Do the Forces Act and What Are the Stresses Developed in a Block That Cause It to Block-cave? Mark A. Smith.........132, 135 Harry A. Leidich........133 McHenry Mosier . .. 133 R. W. Hughes ....... 133 Sherman R. Burdick..... . 133 R. T. Gallagher..........134 C. F. . Price, Jr. ........134 Benjamin F. Tillson.........134 C. F. Jackson......134, 135,137 R. Taborelli...........135 Frank A. Ayer ... .....136 Philip B. Bucky . .........136 Rollin Farmin . . .......136 . . . Weysser.....135, 136, 137 George S. Rice...........137 4. What Determines the Procedure in Removing Caved Ore? Harry A Leidich...........137 McHenry Mosier........137,141 R. W. Hughes...........137 Sherman R. Burdick........138 R. T. Gallagher...........138 Mark . Smith...........138 Philip B. Bucky......140,141,143 C. F. B. Price, Jr..........140 R. H. Bennett...........141 C. F. Jackson..........141, 143 Gerald Sherman..........141 Tell Ertl.............141 .. .. ..................143 C. H. Shoemaker..........143 5. What Are the Criteria for Determining the Efficiency of a Block-caving Operation? Harry A. Leidich.......... 143 McHenry Mosier......... 144 R. W. Hughes........... 144 Sherman R. Burdick.......144 R. T. Gallagher . ......... 144

Jan 1, 1946

By C. R. Clark, G. Swift, D. S. Roberts

The purpose of this investigation was to measure PVT behavior of various types and combinations of heavy hydrocarbon components from the paraffinic, naphthenic and aromatic classes where the relative proportions Of the various components were selected to approximate those of natural gas or gas condensate systems. Synthetic mixtures were used so that the compositions Of the various components could be measured accurately. n-Heptane, methylcyclohexane and methylbenzene were used to represent the paraffinic, naphthenic and aromatic components of the heavy fraction. In the mixtures studied, the heavy fraction composition was held constant at O. O5-mole lraction, the balance being methane except for one mixture where 0.10-mo1e fraction of an intermediate component, propane, was added. The PVT data for the mixtures were determined in a variable-volume, constant-mass apparatus at psuedo-reducedtemperatures from 1.84 to 2.00, over a pseudo-reduced pressure range from 2.3 to 12.0. The experimental results showed that, regardless of the type of heavy material (paraffinic, naphthenic, aromatic, or combinations thereof) mixed with methane or methane and propane, the compressibility factors at equal values of pseudo-reduced temperature and pressure varied by less than 2.2 percent. INTRODUCTION PVT data is used for natural gas and gas condensate fluids in determining reserves of reservoirs and performance of wells, in metering produced fluids, and in recombining samples for laboratory studies. While there are vast amounts of PVT data reported for natural gas and gas condensate systems from which useful correlations have been developed, ' the compositional analyses for these systems and the resultant correlations typically were made with components analyzed through some arbitrary carbon number, usually C6, with the residue reported as a lumped "heavy" fraction. The heavy fraction was stoichiometrically recombined on the basis of an apparent molecular weight to give the final compositional analysis. It is virtually impossible to make a systematic analysis of the effect that variation of the relative amounts of paraffinic, naphthenic and aromatic constituents of the heavy fraction of natural systems might have on PVT behavior. Because there is considerable latitude in the relative amounts of these constituents, one speaks of crudes or condensate liquids as being "paraffin base", etc. It is of interest to determine if changes in the relative amounts of these three types of hydrocarbons in the heavy fraction cause significant changes in PVT behavior. If so, steps should be taken to describe better the nature of the heavy fraction in PVT correlations. If not, more confidence can be placed in the correlations presently employed. DESIGN OF THE EXPERIMENTAL INVESTIGATION We attempted to determine if changes in the base of the heavy fraction would cause significant changes in the PVT behavior of gas or gas condensate fluids. Synthetic mixtures were used to enable us to systematically vary the base of the heavy fraction and to analyze accurately the fluids. We found that the heavy fraction of naturally occurring condensate systems seldom exceeds 0.05-mole fraction. Thus, the mole fraction of the heavy fraction in the synthetic systems studied was set arbitrarily at 0.05, to maximize whatever deviations in PVT behavior that might occur. Further, we judged that since the C7 hydrocarbons normally are present in greater quantities than higher carbon number hydrocarbons in naturally occurring systems, the use of n-heptane, methyl cyclohexane, and methylbenzene to represent the paraffinic, naphthenic, and aromatic species in the heavy fraction would be most appropriate. Finally, to enable us to compare our

Jan 1, 1970

By D. Havlena, A. S. Odeh

The material balance equation used by reservoir engineers is arranged algebraically, resulting in an equation of a straight line. The straight line method of analysis imposes an additional necessary condition that a successful solution of the material balance equatiott should meet. In addition, this algebraic arrangement attaches a dynamic ineuning to the otherwise static material balance equation. The straight line method requires the plotting of one variable group vs mother variable group. The sequence of the plotted points as well as the general shape of the resulting plot is of utmost importance. Therefore, one cannot progrm the method entirely on a digital computer ar is usually done in the routine solution of the material balance equation. If this method is applied, then plotting and anaIysis are asential. Only the appropriate equations and the method of analysis and interpremtion with comments and discussion are presented in this paper. Illustrative field examples for the various cases treated are deferred to a subsequent writing. INTRODUCTION One of the fundamental principles utilized in engineering work is the law of conservation of matter. The application of this principle to hydrocarbon reservoirs for the purpose of quantitative deductions and prediction is termed "the material balance method of reservoir analysis". While the construction of the material balance equation (MBE) and the computations that go with its application are not difficult tasks, the criteria that a successful solution of the MBE should fulfill have always been a problem facing the reservoir engineer. True and complete criteria should embody necessary and dcient conditions. The criteria which the reservoir engineer uses possess a few necessary but no sufficient conditions. Because of this, the answers obtained from the MBB are always open to question. However, the degree of their acceptability should increase with the increase in the number of the necessary conditions that they should satisfy. Generally, the necessary conditions commonly used are (1) an unspecified consistency of the results and (2) the agreement between the MBE results and those determined volumetrically. This second criterion is usually overemphasized. Actually, the volumetrically determined results are based on geological and petrophysical data of unknown accuracy. In addition, the oil-in-place obtained by the MBE is that oil which contributes to the pressure-production history,' while the volumetrically calculated oil-in-place refers to the total oil, part of which may not contribute to said history. Because of this difference, the disagreement between the two answers might be of paramount importance, and the concordance between them should not be overemphasized as the measure of correctness of either one. In this paper, a third necessary condition of mathematical as well as physical significance is discussed. It is not subject to any geological or petrophysical interpretation, and as such, it is probably the most important necessary condition. It consists essentially of rearranging the MBE to result in an equation of a straight line. This straight line method of the MBE solution has invalidated a few long time accepted concepts. For instance, it has always been advocated that if a water drive exists, but one neglects to take it into account in the MBE, the calculated oil-in-place should increase with time. The straight line method shows that in some cases, depending on the size of the neglected aquifer, the calculated oil-in-place might decrease with time. The straight line method requires the plotting of a variable group vs another variable group, with the variable group selection depending on the mechanism of production under which the reservoir is producing. The most important aspect of this method of solution is that it attaches a significance to the sequence of the plotted points, the direction in which they plot, and to the shape of the resulting plot. Thus, a dynamic meaning has been introduced into the picture in arriving at the final answer. Since the emphasis of this method is placed on the interpretation of the sequence of the points and the shape of the plot, one cannot completely automate the whole sequence to obtain "the best value" as normally done in the routine application of the MBE. If one uses the straight line method, then plotting and analysis are musts. The straight line method was first recognized by van Everdingen, et al,2 but for some reason it was never fully exploited. The advantages and the elegance of this method can be more appreciated after a few cases are carefully treated and worked out by it. SOLUTION OF THE MATERIAL BALANCE EQUATION SATURATED RESERVOIRS The MBE for saturated reservoirs written in AIME symbols is

By W. H. McFarland

The mechanical properties have been determined for a large number of alloy-free martensitic steels with carbon contents ranging from 0.08 to 0.20 pct and with manganese contents of about 0.4 to 0.5 pet. These steels were tested 1) as water-quenched, 2) after quenching, temper rolling, and tinning, and 3) after tempering treatments which involved temperatures from 400o to 1300oF and times from 1 min to 8 hr. The majority of these tests represent steel from commercial-size coils, i.e., strip 32 in. wide, coil weights up to 20,000 16, and steel thicknesses from 0.0055 to 0.024 in. As a result of these treatments, it has been shown that as-quenched low-carbon alloy-free steels can be produced with tensile strengths ranging from 140,000 to 220,000 psi and tensile elongations from 3.0 to 4.0 pet in 2 in. The tensile strength of the as-quenched martensites can be represented by the equation, tensile strength (ksi) = 119 + 560 (wt pet C). The response to tempering of these steels is related to previous work by Muir, Averbach, and Cohen and by Grange and Baughman. Strain aging of low-carbon martensite has also been investigated. If low-carbon steels are defined as those steels with a maximum carbon content of 0.2 pet, it is found that the literature on low-carbon, alloy-free martensites contains little data on the mechanical properties of these steels. However, the following facts concerning low-carbon alloy-free martensites seem firmly established:'-' 1) The major factors in controlling the strength of the martensite appear to be a) fine structure, b) the internal strain resulting from the transformation, and, particularly, c) the amount of carbon in solid solution. 2) In low-carbon steels, the martensite is auto-tempered and is in the form of needles with only minor amounts of internal twinning, whereas the martensite in high-carbon steels forms as plates which are internally twinned on a fine scale. 3) Care must be taken in comparing the results of work that has been done on low-carbon steels with varying amounts of alloying elements to data on plain carbon steels. As has been noted by Irvine, Pickering, and Garstone,6 alloying elements generally lower the martensite start temperature and, thereby, decrease the amount of auto tempering obtained during the quench. This makes it difficult to

Jan 1, 1965

Mining and Metallurgy of Lead and Zinc, AIME Vol. 121, edited by Dr. C. R. Hayward in 1936, remains a document of importance today even though 34 years have passed in the meantime. Since nothing in this world seems to be permanent, however, and progress brings new and better ways to do things, a two-volume set has just been published to bring the state of the art of 1936 up to date. This two-volume set, Mining and Concentrating of Lead and Zinc and Extractive Metallurgy of Lead and zinc, incorporates the papers to be presented during the Proceedings of the 1970 World Symposium on the Mining and Metallurgy of Lead and Zinc. The Symposium is being held October 20-24, 1970, in St. Louis, a site near to the famous Lead Belt of southeast Missouri. Some eighty papers are bound in these two volumes covering exploration, geology, mining, concentrating, roasting, smelting, electrolytic processing, residue fuming, refining, etc. All of this is laced with data on tonnages, processes, assays and efficiencies obtained, and the man-hours and equipment needed to achieve these performances.

Jan 1, 1970

By F. Weinberg

The relative concentration of 1" at grain boundaries in controlled orientation bicrystals has been examined by autoradiographic techniques, and by activity measurements of grain boundary surfaces exposed by preferential ,melting. The autoradio-graphs indicate that thallium is concentrated at grain boundaries in as-grown bicrystals, but not in zcell-annealed bicrystals. They also indicate that the solute concentration and the distribution on as-grown bicrystal surfaces are markedly different than that of the bulk material. The boundary surface measurements are in agreement with the autovadiographic evidence. On the basis of these measurements, as-grown bicrystals containing approximately 100 ppm of Tl, solidified at rates between 5 and 30 cm per hr and with tilt boundaries greater than 10 deg, exhibited grain boundary segregation equivalent to roughly 10 atomic planes of pure solute. Higher solute concentrations (equivalent to 140 atomic planes of pure solute) were obtained in bicrystals solidified slowly (0.6 cm per hr); slightly higher values were obtained in specimens containing a large angle nantilt boundary. Annealing for various times over a range of temperatures eliminated grain boundary segregation within the experimental uncertainty of the results (equivalent to 1 atomic Plane of pure thallium at the boundary). The results for the as-grown bicrystals can be qualitatively accounted for by assuming the presence of a groove on the solid-1iq;id interface, at the grain boundary. SOLUTE segregation at grain boundaries may be considered in two parts, namely, nonequilibrium segregation associated with the solidification process, and equilibrium segregation in fully annealed materials.' There is much indirect evidence for nonequilibrium segregation, based on preferential etching at grain boundaries and the mechanical properties of as-cast alloys. In addition, some direct observations have been reported in which radioactive tracers were used as solute additions and segregation detected at the grain boundaries by autoradiographic techniques. However, there is little detailed quantitative data on solute concentrations related to grain boundaries, particularly for different freezing conditions and grain boundary configurations. Equilibrium segregation at grain boundaries has been considered both theoretically and experimentally. cean' has made an estimate of the maximum equilibrium solute concentration that might be expected at a grain boundary, based on the lattice distortions in the boundary region. He arrived at a concentration which was equivalent t a monatomic layer of pure solute. A similar value, based on thermodynamic arguments, was calculated by Cahn and Hilliard for the segregation of phosphorus in iron. Experimentally, much higher values of solute concentration at grain boundaries have been reported recently by both Inman and iler' for phosphorus in iron, and Ainslie et 1.' for sulfur in iron. They observed concentrations equivalent to as much as 20 to 100 atomic layers of pure solute at the grain boundaries. However, in both cases it was shown that the observed segregation was not due solely to equilibrium segregation at the grain boundary. In the former case, precipitation effectss due to trace impurities in the material were believed to account for the large amount of solute present at the grain boundary. In the latter case it was shown that a high density of dislocations in the boundary region could provide a large number of additional sites for solute atoms, other than at the grain boundary. Thomas and chalmera have reported on the equilibrium segregation of po210 in grain boundaries of Pb-5 pct Bi alloys. Using autoradiographic techniques, they observed a concentration of polonium along the boundary trace on the surface of annealed bicrystal specimens grown from the melt. The concentration only appeared after annealing, and varied with boundary angle, increasing as the boundary angle increased. Their conclusions have been questioned by Ward," who pointed out that the segregation they observed along the boundary trace was much too wide to be compatible with the usual concepts of the thickness of a grain boundary of several lattice spacings. Also, Maroun et al.,l1 with specimens similar to those of Thomas and Chalmers, found that segregation could only be detected on the specimen surface, suggesting that Thomas and Chalmers' results were associated with an oxidation effect of polonium, and not equilibrium segregation. Thomas and Chalmers replied12 that they did observed segregation at the grain boundary in the bulk material and suggested further experiments were necessary to resolve the difference. The purpose of the present investigation was to examine both nonequilibrium and equilibrium grain boundary segregation in melt grown bicrystal specimens as a function of boundary angle, growth rate, and solute concentration, and to de-

Jan 1, 1963

By J. R. Long, T. R. Graham

THIS report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. PRELIMINARY WORK In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, 0 to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening, effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By O. D. Sherby, J. E. Dorn

SEVERAL years ago Zener and Hollomon1 suggested that the flow stress of metals might be related to the temperature and strain rate in accord with the functional equation: s=s(eeh/rt) [1] at the same state. The Zener-Hollomon relation also contains the significant tacit implication that the energy for activation, AH, is substantially independent of the state of the material. The utility of this method for correlating creep data with tensile data was illustrated in a preliminary reportL on the effect of alloying additions on the secondary creep rates of binary a solid solutions in aluminum as shown for Al-Mg alloys in Fig. 1. Not only do the secondary creep and ultimate tensile properties for each alloy correlate well on this plot but in addition the activation energy, AH = 17,900 R cal per mol. is identical for the various compositions. Similar types of curves correlating the secondary creep rates at 422°K (300°F) with ultimate tensile data were also obtained for a series of dilute a solid solutions of copper, germanium, zinc, and silver in aluminum. In all cases the activation energy for creep, AH, was found to be equal to about 17,900 R cal per mol independent of the type of alloying element or its concentration. The coincidence of the activation energies for these alloys is probably due to the fact that the activation energies for creep are rather insensitive to small composition changes. Alloying additions, as shown in Fig. 1, however, increased the stress necessary to obtain equivalent values of ee?H/RT. Thus the stress level in curves of the type represented by Fig. 1 gives the relative creep strengths of the various alloys. Inasmuch as these correlations between creep and tensile data were obtained for creep tests at 422°K, it appeared advisable to ascertain the range of secondary creep rates and temperatures over which correlations between creep and tensile data could be made on the basis of the Zener-Hollomon relationship. If, for example, the activation energy changes with different ranges of creep temperatures, the utility of the proposed analysis would be severely weakened. But if AH is constant not only for all dilute alloys, but also over wide ranges of temperature and secondary creep rates, confidence will be developed not only in the broad utility of the Zener- Table I. Chemical Analysis':' and Grain Size of Alloys Mean Grain Residual Impurities. Wt Pct Diam- Alloying Atomic-eter, Element Pct Si Fe Cu Mg Mn mm Aluminum 99.987 0.003 0.003 0.006 0.001 0.25 Magnesium 1.617 0.003 0.004 0.006 0.26 Copper 0.101 0.003 0.003 0.0006 0.001 0.29 Zinc 1.616 0.003 0.005 0.007 0.001 '0.26 * The authors express their appreciation to the Aluminum Company of America for the preparation and chemical analyses of these alloys. Hollomon relationship, but also in its theoretical justification. The following investigation was instituted in order to ascertain the range of validity of the Zener-Hollomon relationship when it is applied to creep and tension data. Materials, Equipment, Technique In view of rather extensive correlatable data now available on the plastic properties of a series of binary a solid solutions of magnesium, copper, germanium, zinc, and silver in aluminum, these alloys were again selected for the present investigation. Previous reports have already covered the tensile properties of these alloys at subatmospheric temperatures," and at elevated temperature," as well as their fatigue properties at atmospheric temperatures, nd their creep properties at 422°K.' Resistivity measurementsa as well as precision lattice constant determinations? evealed that these alloys are a solid solutions. After homogenization. 0.100 in. thick sheets were rolled to 0.070 in. in thickness and recrystallized to about the same grain size. Since the details of these treatments were reported previously," they will not be repeated here. In order to appropriately reduce the scope of creep tests in this investigation only the typical alloys shown in Table I were investigated. All creep specimens were machined such that their tensile axes were in the rolling direction of the 0.070 in. sheet stock. The gage section was 2 in. long and 0.500 in. wide with a reduced section of 3.50 in. Creep strains were measured by means of rack and pinion type extensometers with a sensitivity of 0.005 in. per division. Readings were estimated to 1/10 of

Jan 1, 1953

By E. C. Bain

THE more familiar compositions of iron-carbon-chromium1 and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallographic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

By H. S. Price, D. A. T. Donohue

The system of equations describing displacement of a hydrocarbon liquid by a hydrocarbon vapor in a porous medium where mass transfer takes place between the phases is solved numerically for a variety of gas injection processes. Even though the method of solution is quite general, only systems with three hydrocarbon components are considered. Computer simulations of displacement processes wherein mass transfer between phases is both considered and neglected are compared, and it is shown that neglecting mass transfer can give pessimistic displacement efficiencies. INTRODUCTION The role of the gas displacement process in the recovery of petroleum has been subjected to a series of detailed analyses; as a result, a number of predictive models have been published in the literature. However, because of major simplifying assumptions, most of these models do not completely represent the physical system. As a result, the effect of making the simplifying assumptions is unknown. Therefore, a complete representation of this process — one without major simplifying assumptions —should lead to a fuller understanding of the process, and perhaps to methods of improving it. The general method of developing a model for two-phase fluid flow in a porous medium is to solve simultaneously the continuity equation, the energy equations and the equation-of-state for each phase under the prescribed initial and boundary conditions. For an isothermal system, the energy equations reduce to the momentum equation. Darcy's law. However, since natural gas is the vapor state of the reservoir liquid, interphase mass transfer may take place with concomitant changes in both the intensive and extensive thermodynamic properties of each phase. It is this phenomenon that has often been omitted in previous mathematical models. An additional relation, then, which accounts for mass transfer between the phases, must be included with the other equations to specify a complete model. Completely formulating the equations to be solved is not a difficult task1 but obtaining their solution has been intractable up to now. Availability of large-memory, high-speed digital computers now makes an attack on this formidable problem possible. This paper presents a preliminary study of the problem. Since this investigation is intended to be exploratory, it is restricted to the linear, horizontal, isothermal, two-phase viscous flow of oil and gas in an oil reservoir. In the early development of predictive models of this process, the reservoir system was considered as a unit and various forms of the material balance equation were proposed.2-4 Pressure and saturation gradients were then added in the Buckley-Leverett model.5 The Buckley-Leverett formulation considered the fluids to be incompressible; thus, the mathematical model reduces to a steady-state system. In the 1950's, studies incorporating numerical techniques were being published.6-9 These mathematical models differed in the efficiency of finite difference techniques, the inclusion or exclusion of capillarity or the number of space dimensions considered. To solve these nonlinear, partial differential equations, each phase was considered to be homogeneous with time; therefore, mass transfer between phases was neglected. The effect of mass transfer on the gas displacement process was first reported by Attra. 10 He simulated the one-dimension flow system by a series of cells in each of which the fluids were equilibrated during a time step. In addition, the pressure throughout the system during each time step was predetermined and constant-phase velocities were calculated according to the Buckley-Leverett incompressible fluid flow model. Welge et al.11 developed a model for the displacement of oil by an enriched gas where composition is considered to be a dependent variable. Fluid

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined for the system gadolinium-nickel. Nine intermetallic compounds have been found at compositions corresponding to the following gadolinium-nickel ratios: 3:1, 3:2, 1:1, 1:2, 1:3, 2:7, 1:4, 1:5, 2:17. The GdNi and GdNi5 compounds have congruent melting points of 1300' and 1500°C, respectively while the remaining compounds melt in-congruently. Eutectics exist at 15 wt pct Ni, 31 1/2 wt pct Ni and 87 wt pct Ni with melting points of 6703 8803 and 1220°C, respectively. IN a continuing investigation of the properties of rare earth alloys, a study has been made of the gadolinium-nickel system. Previous work encompassed the iron containing alloys and a subsequent paper will deal with the constitution of the gadolinium-cobalt system. Vogel,1 examined alloys of nickel with lanthanum and cerium. R3Ni, RNi, RNi2, RNi3, RNi4, and RNi5 compounds were found. Endter and Klemm,2 Fulling et al.3 Heumann,4 and Nowotny5 found the 1:2 compositions of this series to exist in a C-15 (face-centered cubic) structure, and the 1:5 compositions in a hexagonal system. Jepson and Duwez6 more recently examined these 1:2 and 1:5 compositions and generally confirmed earlier data while Wernick and Geller7 most recently have given additional data on the GdNi5 compound. Comparisons with our results will be made in the appropriate section of this report. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been given in our earlier paper.8 Chemical analyses of the alloy samples were made by dissolving the specimen in nitric acid, precipitating the gadolinium as hydroxide and the nickel with dimethylglyoxime. Both precipitates were ignited to oxide and weighed. RESULTS Microstructure— Metallography of alloy specimens in this series has been conducted on both arc-melted and annealed materials. Etchants used have been 5 pct nital with approximately 10 pct distilled water added, for high gadolinium samples; Carapella's ferric chloride solution for intermediate compositions; and Marble's (copper sulfate) reagent for high nickel content alloys. Because of difficulties encountered in the grinding and polishing of specimens containing 40 to 75 wt pct Ni, no photomicrographs were made of such specimens. The microstructure of an arc-melted 5.3 wt pct Ni alloy is shown in Fig. 1. Light etching primary grains of gadolinium are embedded in an eutectic matrix. The microstructure of an alloy of 9.55 wt pct Ni alloy, Fig. 2, annealed 50 hr at 700°C, consists almost entirely of the intermetallic compound Gd3Ni. The structure of an arc metal alloy of approximately 19 pct Ni, Fig. 3, consists of grains of the compound GdNi embedded in the Gd3Ni2-Gd3Ni eutectic. The arc-cast structure of the 38.7 wt pct Ni alloy is shown in Fig. 4. Large primary grains of a compound rest in a matrix structure of coarse GdNi-GdNiz eutectic. Because of the occurrence of several peritectic compounds in the central region of the diagram, identification of the primary structure in this alloy is not certain. As has been indicated above, microstructures of alloy specimens containing between ca 40 and 75 wt pct Ni have not been photographed. These specimens were highly brittle, and macro- and micro-cracking were impossible to control in the grinding and polishing procedures. Prolonged annealing did not alleviate this condition. Visual observations in small specimens did, however, provide evidence for a multiplicity of phases and peritectic dissociations of compounds although rationalization of structures was not possible.

Jan 1, 1962

By H. Foster Bain

Jan 1, 1910

By W. N. Lacey, R. H. Olds, B. H. Sage

Samules of liquid and gas were obtained from the primary separator of a well in the Paloma field. The volumetric properties of the samples and of six systematically chosen mixtures of the samples were experimentally determined at 100°, 190°, and 250°F. at pressures up to 5000 lb. per sq. inch. From these data the influence ,of pressure and temperature upon the composition and specific volume of the bubble-point liquid and of the retrograde dew-point gas was established, The formation volumes and gas-oil ratios of the rnixtures investigated were calculated on the basis of the plant-product oil, which is defined as the isobutane and less volatile portion of each mixture. The results are presented in graphical and tabular form. The volumetric behavior of the mixture corresponding to that produced by the well at the time of sampling was determined for 235ºF., the reported reservoir temperature, by graphical interpolation of the experimental data with respect to composition and temperature. The results indicate that the well-production mixture probably existed as a gas at its retrograde dew point under the conditions of temperature and pressure believed to prevail in the producing zone at the time of sampling. The effect upon the phase behavim occasioned by the omission from the well-production mixture of certain components of intermediate molecular weight was investigated. In the first case, all of the isobutane and 11-butane, and substantially all of the iso-pentane, were removed from the mixture of trap samples corresponding to the well production. In the second case, all the propane, isobutane and n-butane, and substantially all of the isopentane, were removed. Both modifications led to considerable increases in the retrograde dew-point Pressure at 235ºF.; an increase of 558 lb. Per sq. in. above that of the unmodified well-production mixture in the first case, and an increase of 1208 lb. Per sq. in. in the second. It was concluded that the material? remaining after the removal of certain components of intermediate molecular weight could not be injected back into the reservoir in the saqe proportion in which they were produced without entailing appreciable loss of liquid material through condensation within the formation. Introduction Under the usual conditions of production practice, petroleum arrives at the surface of the earth in a physical state considerably different from that in which it existed in the underground reservoir. The relative rates of production and the properties of oil and gas measured at surface conditions do not constitute, in general, even a qualitative description of the fluids existing in the reservoir. The estimation of reserves and the attainment of optimum efficiency with regard to rate, quantity, and cost of production require accurate data concerning the physical properties of petroleum throughout large changes in pressure and temperature. Many schemes have been devised for predicting the behavior of propane, as it is encountered in nature? but the experimental work upon which these predictions are based has not, for the most part, been extended to the higher pressures that occur in practice, nor do these methods permit, as yet, the estima-

Jan 1, 1945

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.' Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By Henry Rawdon

Cold-working is generally considered as a process of hardening metals. Diamet-rically opposite statements concerning the applicability of the scratch-hardness method in the testing of cold-worked metals, particularly after severe deformation, which exist in the technical literature led to the study of the results which are summarized in this paper. A series of metals, of which copper, iron and tin are used as illustrations here, were cold rolled to a definite degree without any intermediate annealing and the hardness determined by both the scratch and Brinell methods. The results indicate that the metal hardens rapidly during the initial stages of deformation; however, after a certain stage, which corresponds to a rather definite microstructure, the metal becomes softer and in its final form may be softer than the metal in its initial stage. As part of the study of the scratch-hardness method for metals and alloys in cooperation with one of the technical committees of the American Society for Testing Materials, the authors devoted considerable time to the study of the changes in hardness of metals when cold rolled. Various seemingly contradictory statements in the technical literature concerning the applicability of the scratch-hardness method to such cold-rolled materials were among the principal reasons for the investigation, the results of which are in part presented here. The effect of cold deformation, at least in moderate degrees, on the hardness as measured by the Brinell and other common methods is so well known that further reference is unnecessary. Concerning the scratch hardness of cold-worked metals, Martens and Heyn state' that hardness, whether measured by the ball-pressure method (Kugeldruck) or by the scratch method (Ritzverfahren), will be increased by cold deformation. Jeffries and Archer give a seemingly diametrically opposite view. They state,2 that "the sclerometer (indicating scratch

Jan 1, 1924

By Robert E. Hoffman, John B. Hudson

The self-diffusion coefficient of pure lead has been measured at five pressures between atmospheric and 40 kb. over a temperature range of about 150°C near the melting point at each pressure. Measurements were made using a radiotracer technique, samples being sectioned electrochemically after the diffusion anneal to determine the diffusion penetration curve. Pressure was applied in a "belt" type pressure device similar to that used by Hall et al., in the diamond synthesis. The self-diffusion coefficient, D, can be represented by an equation of the form at constant pressure, and an equation of the format constant temperature. An apparent correlation between the effects of pressure on self-diffusion and on the melting point of the material observed by Nachtrieb et al., at pressures below 10 kb. was found to be only approximate as measurements are carried to higher pressures. OVER the course of the past 30 years a large number of studies1-' of the rate of atom movements in solid metals have been carried out. These studies have in general been aimed at increasing the understanding of the detailed atomic process by which atom movements in metals can take place. The largest portion of these studies consisted of measurements of the self-diffusion coefficient, D, as a function of temperature. From such studies con- siderable information regarding the energetics of the motive process has been deduced. Recently such measurements have been extended to the pressure dimension. However, the existing work in this area is scanty and has in the past been limited to the pressures attainable in oil or gas bombs—i.e., up to about 10 kilobars (kb). In the present work, the self-diffusion behavior of pure lead has been investigated using the "belt" type high-pressure apparatus designed by Hall7 over a pressure range from atmospheric to 40 kb at temperatures extending over about a 150°C range close to the melting point at each pressure.

Jan 1, 1962

By W. A. Griffith

Fractional replication of factorial design, a general method for planning experimentation and for analysis of data obtained, is described as applied to a flotation investigation. This method leads to determination of optimum process conditions with minimum experimental effort. Its advantages over simple factorial design are demonstrated. A METHOD for planning experimentation and for analyzing the data secured will be demonstrated. This method, termed fractional replication of factorial design, employs a relatively small number of individual experiments to determine which of a large number of process variables are controlling, to determine which combination of levels of these variables is most likely to produce optimum results, and also to predict what results will be obtained with a particular combination of conditions not already tested. Although the general method is not new, having been developed by Finney in 1945,' the extent to which it can improve the effectiveness of applied research generally has not been recognized by metallurgists. The fractional replication procedure is particularly useful in flotation experimentation and an example from such an investigation will be used in the paper. However, it has equal value in any investigation in which similar experimental difficulties are encountered. In developing a flotation process for a particular mineral separation, the investigator is inevitably confronted with the following difficulties: 1—There are a large number of potentially important process variables. 2—Results of individual experiments are not highly reproducible, due in part to the difficulty in precisely controlling all the variables. 3—Considerable effort is expended in conducting individual experiments. 4—There are practical limits on the number of individual experiments which can be made. In situations of just such a type, modern statistical methods of planning experimentation and analyzing data have their greatest value. Applications of one such technique, called factorial design, to problems of this type have been described by Dorenfeld and others.'-' The simple factorial design is an efficient procedure when the investigator hopes to provide a comprehensive understanding of the effects and interrelationships of a small number of variables over a limited range. In applied research, this is seldom the main objective. Rather, the investigator usually wishes to determine which of the many potentially important variables are in fact controlling, which levels of the controlling variables will provide opti- mum metallurgical results, and what these results will be at optimum conditions. Interest in detailed trends is limited to the controlling variables and to levels in the region of optimum conditions. Simple factorial design has serious deficiencies for such objectives and is not the most efficient method of experimental design. Deficiencies of Factorial Design In a simple factorial design, an experiment must be made at every possible combination of each level of every variable, once these have been chosen and the levels of each to be included have been decided upon. As the number of variables or levels of each increases, the experimental program quickly reaches prohibitive size. For example, an investigation of only four variables, each at four levels, requires 256 individual experiments. Often upon completion of such an extensive program, it is found that one or more of the variables has metallurgically unimportant effects or that a poor estimate has been made as to the appropriate range of levels to be investigated. The result is that only a small proportion of the data obtained falls in the range of real metallurgical interest. Indeed, it frequently can be anticipated that certain combinations of levels of variables will not produce results of interest, but they still must be included so that the essential balance, or orthogonality, of the design will be retained. It may be true that factorial design will provide the greatest amount of information from a given number of experiments, but it does not necessarily follow that it will lead to the desired information with a minimum number of experiments. Much of the information provided may be of little value. Advantages of Fractional Replication The disadvantages of simple factorial design are overcome to a great extent by a modification known as fractional replication. This is a technique for sampling systematically the potential data of a full factorial experiment, that is, the data which would have been obtained if the complete factorially designed program had been completed. Only a fraction of the total array of experiments is made, but the experiments are chosen in such a way that the important advantages of factorial design and the accompanying analysis of variance are retained. The data obtained from the first group of experiments are used to determine which of several variables are controlling and which levels of these variables are most likely to produce the desired result. Unimportant variables and levels of variables then may be

Jan 1, 1956

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963