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By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer' up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der' found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.'' APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

By Burt Hartmann

The nation's ever-expanding construction and mining activity has placed an increasing demand upon engineers and geologists to design and construct stable slopes in earth materials-soil and rock. Man's attempt to handle these slope stability problems has been based primarily on practical experience and the resulting theories formulated to explain the phenomena. Too many instances occur when man is faced with a slope stability problem that has not yet been experienced and doesn't lend itself to solution by any existing theory. At this point he must extend himself in using his engineering judgment to arrive at a reasonable and safe design. As past experience has shown, all of the "safe designs" are not really safe. Sometimes they result in embarrassing failures. Measurements provide the key to understanding and controlling natural phenomena. We cannot hope to gain control of the slope stability problem until we understand the causes of slope failure, their behavior with respect to time and their relative magnitudes. Measurements required for an adequate definition of any slope problem must be of the highest reliability because of the importance of decisions which must be based on them. For this reason, direct measurements of movement, shear strength, water pressure, etc. of the unstable mass are preferable to indirect measurements of other physical properties. Movement instruments which can be positioned inside of the slope mass (within boreholes) are among the most useful in diagnosis and/or monitoring of slope movements. The higher the sensitivity and il-measurement precision possible with borehole instruments, the quicker the required information can be obtained and the more exactly may hazardous conditions be observed. A high density of measuring points in a single drill hole is deemed essential for diagnostic purposes. Behavior gradients may thus be obtained. The Pressure Meter (Fig. 1) can be used to measure a relative strength

Jan 1, 1968

By William L. Fink

Nickel is used as an alloying element in several complex commercial aluminum alloys, among which are found some very interesting properties, such as relatively high strength at elevated temperatures, relatively low coefficient of expansion, the absence of permanent growth, ability to take a good polish, and a bright, pleasing as-cast surface. For that reason the aluminum-nickel system was included in the list of binary aluminum systems that are being studied as a preparation for the investigation of more complex commercial alloys. This paper is the fifteenth of a series from the Research Laboratories of the Aluminum Company of America reporting the results of investigations of equilibrium relations in aluminum-base alloys of high purity. The aluminum-nickel equilibrium diagram from 0 to 18 per cent nickel was determined, using the purest material available. Previous Investigations The entire aluminum-nickel system was studied thermally and microscopically by Gwyer.1 At the aluminum end of the system he found the intermetallic compound NiA13. He found a eutectic at 6 per cent nickel with a melting point of 630" C. A slight thermal arrest, which he could not explain, was also noted in alloys from 2.5 per cent to 41.9 per cent nickel at 550" C. Bingham and Haughton,2 in a later investigation of alloys of aluminum with copper and nickel found the eutectic concentration of the binary aluminum-nickel system at about 5.3 per cent nickel. The melting point of the eutectic was about 633" C., or slightly higher than that found by Gwyer. Although the solid solubility of nickel in aluminum could not

Jan 1, 1934

By Alwyn Birchmore Cox, Ian William Wark

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers' in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950

By William Ian Wark, Alwyn Birchmore Cox

DIFFERENT parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. EXPERIMENTAL METHOD The methods used have been described previously.1-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution ' composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1938

By Heinrich Ries

In another place,* the writer has called attention to the modern methods of the laboratory investigation of clay, and it is desired here simply to discuss one branch of the subject, which, though of considerable importance, has heretofore received little attention in this country, viz., the rational analysis of clay. In order, however, the better to point out the bearings and advantages of this procedure, it is necessary to refer briefly to the ultimate analysis as well. The remarks in this paper refer only to the use of clay for the manufacture of clay-products. Pure clay or kaolin-f is extremely refractory, possesses little plasticity, and usually shrinks aud warps considerably in burning. Even the smallest proportion of impurities changes these properties, so that the kaolin exhibits variations in shrinkage, plasticity, tensile strength, fusibility, and often color when burned. The majority of nearly pure kaolins consist of kaolinite (A1,O2 2SiO,, 2H20), undecomposed feldspar, and quartz. The kaolinite generally forms the finest particles of the clay and is known as the clay-substance, while the rest of the clay-particles are collectively spoken of as sand. In the ordinary or ultimate analysis, the substances generally determined are silica, alumina, ferric oxide, lime, magnesia, alkalies and water. An analysis of this type simply regards the clay as a mixture of elements or oxides, but gives no clue as to the actual condition in which these substances exist, i.e., whether as silicates, oxides or carbonates, etc., a point which it is of the highest importance to know; for the individual components of the clay influence its properties not only according

Jan 1, 1899

By E. Gregory, A. Coucoulas

Carbm dioxide, which exists metastably as a constantly subliming molecular solid in a normal room-temperature environment, has been shown to exhibit many microstructural features which are similar to those observed in metals and ceramics at temperatures approaching their melting points. An examinution has been made of some of the factors affecting a brittleness condition known as "smzdiness" which occurs in solid carbon dioxide. It has been shown to be highly dependent on manufacturing and storage conditions and is thought to be a marked intergranu-lay brittleness which results from a combination of excessive grain growth and a concentration of gas-filled pores at the grain boundaries. In the course of an investigation carried out to explain certain physical and mechanical properties of solid carbon dioxide, observations were made of the microstructure and fragmentation of samples after fabrication and storage under varying conditions. Many similarities between the structures of solid carbon dioxide observed under ambient conditions and those existing in metal and ceramic systems at temperatures approaching their melting points have been observed. There are, however, important differences between solid carbon dioxide and the common metallic and ionic solids which result primarily from the differences in the nature of the bonding forces. Despite these differences, the relative ease with which certain microscopic observations can be carried out, may make solid carbon dioxide a useful material model for the physical metallurgist and the ceramist. It could also prove a valuable material for educational purposes where it is required to illustrate grain phenomena which normally can only be seen with the aid of a high-temperature microscope, and after prolonged chemical or thermal etching.

Jan 1, 1963

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By J. W. Whalen

The design, operation and evaluation of an instrumental method for the determination of fluid saturation in porous materials during multiphase flow studies is described. The presence of a magnetic tracer comprising approximately 20 per cent by weight of the aqueous phase is necessary in the utilization of this method. The results of two-phase relative permeability studies on two samples of porous media are presented. The realizable accuracy of the magnetic susceptibility apparatus in fluid saturation determination is estimated to be 2 saturation per cent. The response characteristics of the instrument, together with its simplicity of operation and maintenance are sufficient to recommend its use in routine laboratory studies. INTRODUCTION The problem of fluid saturation determination in laboratory multiphase flow studies characterizing oil recovery processes is one which has been given exhaustive study. Briefly the requirements which are considered essential for a method sewing this purpose are: (1) that the measurement be made external to the porous rock sample under study with no interruption of the fluid flow pattern, (2) the saturation indication must be independent of fluid distribution in the volume scanned by the measuring device, (3) the sensing element should have a small field of definition enabling several independent measurements to be made along the length of a core sample, and (4) the properties of the fluid phases should not be too greatly influenced by required tracer substances. Several methods of saturation determination have found acceptance as meeting most of the above requirements. These include resistivity,1 X-Ray absorption,2,3,4 radiotracers,5,6,7 and neutron8 diffraction The merits of these techniques have been discussed elsewhere in detail and will not be considered here. It may, however. be pointed out that the elaborate instrumentation required by the methods mentioned above, with the exception of the resistivity method (which is undesirable from other standpoints) encourages the development of methods of saturation determination which, while meeting the requirements listed, are simple to operate and maintain. It is the purpose of this paper to describe the instrumentation and evaluation of a technique for the determination of fluid saturation which combines relative simplicity with an accuracy and applicability comparable with methods now in practice. DESCRIPTION OF THE METHOD If the magnetic susceptibility of one of the fluid phases contained within a porous material is sufficiently greater than that of the remaining phases, the fluid content of the material with respect to that phase may be determined by an induction measurement. This may be accomplished by measuring the induced voltage in the secondary of a transformer which contains the porous sample and its interstitial fluids as a portion of the magnetic flux path. Since the fluids used in multiphase flow studies involving petroleum reservoir samples possess uniformly low magnetic susceptibilities, the use of a magnetic tracer in one of the fluid phases is required. In view of the relatively high paramagnetic susceptibility of salts of the transition elements, together with their high water solubility. these compounds become logical choices as tracer materials. Cobaltous chloride, having a specific magnetic susceptibility of 17.5 x 106 cgs electromagnetic units, was used as the tracer material throughout this work, in a concentration of approximately 20 per cent by weight in the aqueous phase. MAGNETIC SUSCEPTIBILITY APPARATUS Basically, the magnetic susceptibility apparatus consists of a transformer serving as the detecting head, a

Jan 1, 1955

By L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,' have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson' have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive

By A. Manganwidjoyo, W. A. Wiebenga

The aim of this paper is to disclose some of the correlations between rock parameters, hidden in Wuerker's "Annotated Tables of Strength and Elastic Properties of Rocks," 1956. The empirical relations concern dry rocks of varying porosity. Curves and equations interrelating the specific gravity, compressive strength, bar velocity, and Poisson's ratio are presented. In 1956 Wuerker published his "Annotated Tables of Strength and Elastic Properties of Rock", in which various physical properties of rocks determined by different authorities, are tabulated systematically. The tables are primarily intended for use by mining-, quarrying- and ore-dressing engineers. Since the list of measured parameters for each type of rock includes properties such as — grain size, specific gravity, porosity, compressive strength, static elastic cons:ants (moduli of elasticity, rigidity, specific damping capacity and longitudinal bar velocity) the tables are also of considerable interest to the practical geophysicist. Correlations between rock parameters may enable geophysicists, geologists and civil engineers to transiate measurements from one parameter to another. Even if these translations are of limited accuracy, or valid only within certain specified ranges, they often serve a useful parpose. The aim of this paper is to disclose some of the correlations between rock parameters concealed in wuerker's Tables. Throughout this paper the following symbols and units are used unless otherwise stated: Sg is Specific gravity, the ratio of the density of a specimen to the density of water at 4°C. P is Porosity, in %, the ratio of the volume of voids in a specimen to its total volume. CS is Compressive strength in 1000 p.s.i., the stress under which a specimen will fracture when undergoing a standard compression test. V is Bar Velocity in kilo-feet/sec, the velocity of longitudinal seismic waves measured in a slender bar type specimen. Vc is Bulk or Constraint Velocity in kilo-feet/ sec, the velocity of longitudinal seismic waves measured in a very large specimen.+is Reciprocai bar velocity in millisecs/ft (1 millisec = 10-3 sec). cis Poisson's ratio, the ratio of the lateral to longitudinal strain of a body under longitudinal stress. CORRELATIONS Specific Gravity (Sg) vs. Porosity (P) Figure 1 is a diagram illustrating the relatiooship between specific gravity and porosity for approuirr~ately 70 samples of dry rocks. A curve fitted by estimation to this data yields the empirical formula: Sg =-0.0268P + 2.67 * 0.2 (1) Considering unit volume of a porogs specimen then

Jan 1, 1961

By W. A. Sweet

The furnace I am now about to describe was designed to obtain and maintain very high temperature. Knowing the cost of the gas furnace that was in successful operation here and abroad, I approached the subject with some misgivings as to my ability to attain anything like success, or even to reach a point of advancement. There seemed to be a field for a furnace of moderate cost for small mills, or where a particular heat was wanted, but the work was not enough to warrant the outlay necessary to build any gas furnace yet brought before the public. The section, Plate V, represents the furnace as I now build it for

By W. A. Sweet

THE furnace I am now about to describe was designed to obtain and maintain very high temperature. Knowing the cost of the gas furnace that was in successful operation here and abroad, I approached the subject with some misgivings as to my ability to attain anything like success, or even to reach a point of advancement. There seemed to be a field for a furnace of moderate cost for small mills, or where a particular heat was wanted, but the work was not enough to warrant the outlay necessary to build any gas furnace yet brought before the public. The section, Plate V, represents the furnace as I now build it for

Jan 1, 1875

By Lyman Johnson

Single crystals qf copper in "single slip" orientatiorzs have been deformed in compression. During defortnation all of the independent deformation parameters have been measured. These parameters consist of thefive strain components and three components descrihing the lattice rotation. By a finite strain analysis these pararmeters , forrming a deformation gradient martrix, are related to the amounts of slip on each of the twelve slip systems. The results show that the amount of secondary slip is about equal to the amount of primary slip. This is an order of magnitude larger than has been believed previoutsly. ACCORDING to early theory and experiments, when a single crystal of a fcc metal is deformed in tension or compression it should deform by slip on only one slip system until the stress axis reaches a symmetrical orientation.' However. the observation of a large increase in the secondary dislocation density during ..single slip" makes it clear that some slip does occur on secondary systems. Knowledge of the amount and distribution of this secondary slip is essential to a complete understanding of the mechanisms of single-crystal deformation. Ahlers and Haasen 2 and Mitchell and Thornton1 have tried to detect the amount of secondary slip in single crystals of silver and copper, respectively. Each simultaneously measured the angle A, between the tensile axis and the primary slip direction and the length 1 of a gage section of the specimen after incremental amounts of deformation in tension. The measured A, was then compared with the theoretical single slip angle hp. given by sin Ap = j sin . hO where ?o was the initial angle between the tensile axis and the primary slip direction and lo was the initial gage length. In both sets of experiments a small but systematic difference between ?e and ?p was found. This difference must be due to the occurrence of secondary slip. However, as Mitchell and Thornton1 pointed out. nothing quantitative can be said about the amount and distribution of this secondary slip from the measurements that they made. The reason that no quantitative conclusions could be made is because no unique solution for the distribution of slip on the twelve fcc slip systems can be determined from only two measured deformation parameters such as A and 1. There are, in fact, eight independent macroscopic deformation parameters that can be measured when a single crystal undergoes a homogeneous deformation. Physically these can be thought of as the five finite strain components and the three angles describing the crystal lattice rotation. All eight of these parameters were measured by Taylor4,5 for aluminum deformed in tension and compression. At that time the concern was to show that slip occurs on {111 (110) systems in fcc metals, and the mathematics were not available to determine what slip distributions were compatible with the measurements. In this paper the mathematics6,7 are developed that allow the slip distribution to be determined from these measurable macroscopic deformation parameters. The analysis is applied to the measurements of the strain and lattice rotation of copper single crystals deformed in compression. The results show that the amount of secondary slip is an order of magnitude larger than had previously been thought. CRYSTALLOGRAPHIC DESCRIPTION OF A HOMOGENEOUS DEFORMATION The deformation of a solid body can be represented by a transformation matrix F that transforms the un-deformed state into the deformed state. Consider a vector X connecting two material points in the unde-formed material and the vector x connecting the same two material points after deformation, where both vectors are referred to the same set of Cartesian axes. The final vector x is related to the initial vector X by the equation: X = FS. [2] Eq. [2] can be considered as the equation defining F, which is called the deformation gradient matrix. Its components are: If the deformation is homogeneous, the transformation is linear and the components of F are constants. Using subscript notation, if P is the unit vector in the initial direction of a material line, the components of the unit vector p in the direction of the same material line after deformation are given by:

Jan 1, 1970

By T. J. Koppenaal, M. E. Fine

The critical resolved shear stress of aCu-A1 single crystals has been investigated as a function of composition, testing temperature, and strain rate. The strength, and its temperature and strain rate dependency increase markedly with aluminum content. The solid solution strengthening at 4.2°K is much larger than at room temperature. The activation energy for the low temperature dislocation cutting process increases from about 0.17 ev for a 0.5 at. pct A1 alloy to about 0.50 ev for a 14 at. pct A1 alloy. This result is attributed to an increase in the width of extended dislocations due to the known decrease in the stacking fault energy. In addition, the activation volumes at 4.2 and 77°K decrease with aluminum additions. Concerning the solid solution strengthening in the 296° to 373°K range, no definite conclusions are reached, but it is suggested that subgrains and cutting of subgrains are important. In a previous paper,' the authors reported that adding aluminum to copper produces two types of strengthening: a yield point effect and an increase in the lower yield stress. This behavior is illustrated in Fig. 1 by shear stress-shear strain curves of furnace-cooled single crystals of pure copper and Cu-14 at. pct A1. The yield point effect, At, was thoroughly studied previously1 and shown to be associated with short-range order. The present paper reports an investigation of the lower-yield stress in aCu-A1 single crystals as a function of composition, testing temperature, and strain rate. EXPERIMENTAL PROCEDURE Single cryski1 tensile specimens were prepared in the same manner as previously described.l Briefly,

Jan 1, 1962

By G. V. Cullen, N. G. Siviour

It has previously been reported that metal loadings of up to 6.8 m. eq/g. of dry coal can be obtained by contacting brown coal or lignite with ammoniacal solutions of ammine forming metals. Application of equilibrium expressions to further experimental results indicates that the extraction is by ion exchange, that the exchange is divalent-univalent for Zn, Cd and Ni, but is mainly univalent-univalent for Cu, and that to obtain reasonably uniform values for the equilibrium constants correction formulae must be applied to compensate for multiple functionality of the coal and its pH dependence in ion exchange. The results are shown to be consistent with the hypothesis that metal ammine complex cations are exchanged for protons derived from carboxyl and/or phenolic hydroxyl groups in the coal.

Jan 1, 1981

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

By D. C. Hilty, W. Crafts

L. S. Darken—Laboratory investigation of deoxidizing and other steelmaking reactions is usually centered, at least first, on the determination of the equilibrium or equilibria involved. This seems a reasonable procedure since equilibrium, if attained, depends only on composition, temperature, and pressure; hence conclusions derived from data on small experimental quantities are applicable to a heat of steel providing eauilibrium is attained in both cases. A knowledge of equilibrium serves as a useful framework even though we may know that practical conditions do not correspond to complete equilibrium. On the other hand, nonequilibrium or rate phenomena depend on a wider variety of conditions and are more difficult to interpret; conclusions applicable to laboratory conditions may or may not apply to larger scale phenomena. Hence the attainment or nonattainment of true equilibrium in the experiments here reported is of critical importance in evaluating their significance. Since some of the statements in this paper and in the closely related preceding one (on aluminum deoxidation) imply some doubt on this matter, I should first like to ask the authors whether their conditions are intended and believed to represent equilibrium. I should like to point out three considerations which seem to cast considerable doubt on the achievement of equilibrium, at least of the particular equilibrium under consideration. 1. In the experiments on manganese deoxidation the authors point out that they could not maintain the manganese-oxide slag on top of the metal in their rotating crucible, and hence they substantially dispensed with this slag. This leads to serious trouble in the interpretation of the results, for any equilibrium is, of course, a particular specific equilibrium—in this case Mn + O = MnO The experimental deletion of the upper layer of manganese oxide means that if equilibrium is attained at all it is attained between the metal and the MnO which has soaked into or adhered to the crucible (under the metal) and has dissolved substantial amounts of the crucible material including impurities. These impurities may constitute a significant portion of the slag by virtue of the small total amount of slag, even though the crucible is relatively pure. Hence there would seem to be a strong presumption that the equilibrium (if attained) involves not a pure MnO (or MnO — FeO) slag but one saturated with alumina and containing perhaps considerable impurities which substantially lower the concentration and activity of MnO, causing the above reaction to proceed to the right further than it would in the absence of alumina and impurities. Hence it is not surprising that manganese here appears as a better deoxidizer than found by other investigators. The present results may represent equilibrium with a slag of unknown composition which seems unlikely to be particularly related to plant experience. 2. The curves representing the observed silicon deoxidation (figs. 3, 4, and 5) are all drawn with a discontinuity in slope at about 0.02 pct oxygen. This point is interpreted as corresponding to the three-phase equilibrium, metal, slag, solid silica. The type of construction shown in these figures (though apparently fitting the data) is contrary to a fundamental principle of heterogeneous equilibrium as pertains to the construction of phase diagrams. According to this principle, the two solubility curves (each of the two portions of the curves in figs. 3, 4, and 5) must intersect in such manner that their (metastable) extensions must lie outside the homogeneous field rather than inside as in these figures. In other words, the "point" in these curves should be aimed in the opposite direction, if it is to be interpreted as corresponding to the three-phase equilibrium. The construction adopted is in violation of the second law of thermodynamics. This matter is discussed in detail in several texts and also by Lipson and Wilson.&apos;" The same criticism applies to the later figures representing conditions for manganese additions. The occurrence of this discontinuity or break at 0.02 pct oxygen casts further doubt on its interpretation. The earlier investigation of this system by Korber and Oelsen is in substantial agreement with the several recent findings of Chipman and coworkers that the oxygen content of iron in equilibrium with silica and silica-saturated iron oxide slag is about one third to one half that (0.24 pct at 1600") of iron saturated with pure iron oxide; thus there seems reliable evidence that iron saturated with silica and iron silicate slag at 1600" contains about 0.1 pct oxygen, or certainly much more than the 0.02 pct proposed in this paper. 3. In the quarternary system iron-silicon-manganese-oxygen one of the equilibria involved may be written 2 Mn + SiO2 (solid) = 2 MnO <slag> + Si The activity of SiO, is constant (if equilibrium is attained) by virtue of its presence as a substantially pure solid. At not too low metallic manganese content, the activity of MnO in the slag is constant by virtue of the fact that the slag is substantially pure manganese silicate saturated with silica and hence of constant composition. Thus the equilibrium constant for the above reaction is asi/a2Mn. Barring unanticipated large changes in the activity coefficients, the equilibrium constant may be adequately approximated for the composition range covered as [% Si]/[% Mn]2. Thus a plot of log [% Mn] against log [% Si] would be expected to be linear with a slope of one half as found by Kijrber and Oelsen. In the present investigation the slope (shown in fig. 15) is found to be one. It is difficult to believe that this finding represents a correct equilibrium determination, since it is at odds both with prior experimental investigation and with. theory. In view of the above points it seems that, although this paper reports many interesting findings, there is room for considerable skepticism as to the attainment of equilibrium and as to the conclusions drawn. N. A. Gokcen—The authors consider that Si% x O2% product is constant. This product is a function of the asi X a0 activity of Si02. The true constant is -------------. If the asio2 slags of this investigation were always saturated with SiO2 then Si% X O2% product would be constant,

Jan 1, 1951