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By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By F. Windolph

There are no hard and fast rules for building tailing dams, and each case has to be analyzed individually because of special conditions encountered at each location. Certain criteria are used for building dams at Climax, Colo., where they must be placed in rather steep mountain valleys on foundations that are practically impermeable. The tailing is relatively coarse, and a coarse fraction stays near the berm where it is deposited, while most of the fines flow with the water to the pool. Thirty years experience has led to certain design for toe dams, decanter lines and towers and tailing dams. A new tailing disposal area, started at Climax in 1958, will ultimately have a height of 495 ft and impound about 300 million tons. The following applies to the construction of this new tailing area.

Jan 11, 1961

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By C. A. Siebert, O. S. Duffendack, A. W. Herbenar

IN metallurgical problems involving the study of equilibrium in binary systems, the ,existence of an additional vapor phase, due to the presence of a volatile component in the alloy, has often been neglected. This is well indicated by the modified form of the phase rule, usually accepted in condensed systems in which pressure is not considered as a degree of freedom. In many cases the vapor pressure of the volatile component is exceedingly small and for all purposes can be considered negligible, in which case this form of the phase rule is applicable. However, alloys containing Hg, Cd, Zn, or Mg, tend to show very marked equilibrium vapor pressure, even in the solid state, and therefore present cases where the modified form of the phase rule no longer holds true. A quantitative determination of the vapor pressure of zinc in alpha brasses is not only of practical interest because of the loss of zinc in the processing of these alloys, but also of theoretical interest in that such measurements provide a means of applying the principles of theoretical physics and physical chemistry to problems of applied metallurgy. A number of investigators have reported vapor pressure measurements of zinc in alpha brasses. Hargreaves1 made extensive measurements which were used by Birchenall and Mehl² and Guttman³ for the determination of activity coefficients of zinc in alpha brasses. Hargreaves1 used a differentially heated quartz tube and measured the condensation temperature at one end corresponding to the temperature of the heated brass at the other end. Birchenall and Cheng outlined the condensation method of obtaining vapor pressure of zinc and Cd over some of their silver alloys." The primary object of the present investigation was to increase the range and accuracy of the vapor pressure data for the alpha brasses. Preparation of Alloys: Six alloys were prepared from Bunkerhill zinc and O.F.H.C. copper, both of 99.99 pct purity. The cast ingots were annealed for 24 hr at 550°C, scalped, cold rolled 40 pct and annealed for 50 hr at 550°C. The annealed bars were then surface ground and degasified for 30 min at approximately 550°C in an induction heated vacuum furnace. The surface of the bars was removed before milling the bars into relatively fine chips for chemical analysis and samples for the equilibrium cell. The analyses of the six alloys are given in table I. Experimental Method: The vapor pressure of zinc over the various alloys at a number of temperatures was determined from absorption spectra data. The spark source was produced by means of a high tension discharge between two electrodes of pure zinc. The design of the absorption vessel is shown in fig. 1. The vessel was constructed of transparent quartz which transmits the whole of the visible spectrum and the ultraviolet down to a wave length of 2000 A. The thickness of the vapor space was set at 0.8 mm so as to permit a relatively wide range of measurements without altering the vapor space, and thereby necessitating recalibration of the vessel. The furnace used for heating the absorption vessel consisted of a split wound furnace as shown in fig. 2. The spectrograph used in obtaining the transmitted zinc spectra was a double prism type especially designed for a region of 2500-3500 A. A step diaphragm used in conjunction with a tungsten filament provided the necessary intensity patterns required for calibration of the photographic plates.

Jan 1, 1951

By William E. Ford, Edward Salisbury Dana

430. The more important of the special properties of a mineral species with respect to heat include the following: Fusibility; conductivity and expansion, especially in their relation to crystalline structure; change in optical characters with change of temperature; specific heat; also diathermancy, or the power of transmitting heat radiation. The full discussion of these and other related subjects lies outside of the range of the present text-book. A few brief remarks are made upon them, and beyond these reference must be made to text-books on Physics ant1 to special memoirs, some of which are mentioned in the literature (p. 305).

Jan 1, 1922

By Horace C. Knerr

It has been shown that the resistance to corrosion of duralumin sheet is greatly influenced by the quenching medium used in heat treatment, or, more specifically, by the rate of cooling during quenching. The severity of corrosive attack after exposure to salt-water spray increases in .the following order: The tensile strength, yield point and elongation are only slightly affected by the quenching medium, as shown in Table 1. Tensile test requirements: yield stress, 25,000 lb. per sq. in. minimum; ultimate stress, 55,000 lb. per sq. in. minimum; elongation in 2 in., 18 per cent. minimum.

Jan 1, 1931

By L. M. Howe, J. Gordon Parr, E. Saarema

THE decreasing solid solubility limit at the titanium-rich end of the Ti-Cu constitutional diagram,' Fig. 1, suggests the possibility that titanium-rich alloys may be age-hardenable. However, results obtained by Holden et al. reproduced in Fig. 2 show that after quenching from 790°C the age-hardening of an alloy containing 1.7 pet Cu is very slight, while a 0.8 pet alloy decreases in hardness, during heat treatment at 400°C. It was believed possible that powder samples of alloys might show different results from the lump samples used by Holden et al., since small particles are often more sensitive to diffusion processes than larger samples. Consequently, a 1.9 pet (by weight) Cu alloy was made by the technique of levitation melting," checked for homogeneity, and filings of 48-65 Tyler screen size were cut from it for aging experiments. The filings were helium-quenched (by a technique described previously)' from 790°C, sealed in vacuo in silica tubes and aged at temperatures of 400°, 450°, and 500°C. Microscopic and X-ray examinations failed to reveal any structural changes during the aging process. This is not too surprising since early stages of precipitation do not usually manifest themselves in ways that are readily detectable by metallographic methods, and the extent of precipitation on overaging a 1.9 pet alloy is very small. However, hardness readings (taken on a Bergs-man micro hardness tester, using a 25 g load applied to a diamond indenter) do show a hardness peak at each aging temperature, Fig. 3. About a dozen readings were taken on each heat treated sample; the highest reading and the lowest reading were ignored and an average taken of the remaining values. In

Jan 1, 1957

By Charles M. Means

A thoroughly modern coal-handling system has been installed at the Pittsburgh Terminal H. H. &. Coal Co.'s new No. 8 shaft, or Cover-dale mine, about 11 mi. (17.7 km.) from Pittsburgh on a spur of the Montour R. R. The Pittsburgh scam, which is the one worked, is reached at a depth of 342 ft. (104 m.). Power is delivered to the mine at 22,000 volts over a transmission line of the bow-arrow type of construction. A private telephone line connecting the various mines and the main office in Pittsburgh is carried on the same poles. The high-tension line is brought to an outdoor, step-down, transformer substation, where three 833-kv.-a., single-phase, 60-cycle, oil-insulated, self-cooled transformers reduce the potential to 2300 volts. The transformers are protected by electrolytic, aluminum-cell lightning arresters, horn gaps, and choke coils. High and low-tension busses, together with fuses, choke coils and air-break horn-gap switches with thcir remote-control operating mechanism are mounted on a substantial structural-steel tower 25 ft. (7.6 m.) in height. Mine Substation The transformer substation is adjacent to a. pressed-brick building that houses direct-current substation equipment together with switchboards, etc., for the control and distribution of power. This building also contains the hoist for the men and supplies. Main Switchboard The 2300-volt circuit is carried underground in a conduit from the transformer substation to an oil switch in the substation and supply hoist building. This is the main switch controlling the 2300-volt busbars mounted back to a twelve-panel black-slate switchboard. From the switchboard, 2300-volt circuits are carried to transformers feeding the street and house lighting systems and to other transformers furnishing power for the elevator and lighting circuits in the store building. Other 2300-volt circuits run from this switchboard to the main hoist building, fan house and auxiliary or man-and-supply hoist. High-tension wiring,

Jan 1, 1922

By C. C. Spencer

A CHARGE of 12,200 lb of scrap was used on all heats. The slag materials that were added to the furnace along with manganese ore were kept constant; that is, 230 lb Coxey sand was put on the banks at the slag line before each heat was charged, 35 lb limestone was added after the carbon boil. manganese ore was the only item varied in the four series described herein. I might add here that it is impractical for us to get the carbon clown in one boil, for the steel would come out through the doors and run over the floor. We take the carbon down in two vigorous boils.

Jan 1, 1947

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By Gordon C. Rausser, Michael D. Boehlje, Richard A. Levins, John A. Otte

Changes in SO2 emission standards will not only influence the cost of supplying energy demands from coal, but also the competitive position of various production regions and the method of mining (surface vs. underground). A multiperiod interregional competition model was utilized to evaluate the interactions between mining capacity, new mine development, coal reserves, mining, processing and transportation costs and equipment availability and SO2 emission standards. The empirical results indicate that not only will costs increase dramatically, but production in eastern as well as western regions that have low sulfur reserves will also increase as sulfur standards become increasingly more strict. Implications of the adjustments in the location of coal mining activity for the processing, transportation, and capital goods markets are also presented.

Jan 1, 1978

By J. T. Dewan

An experimental setup is described whereby the responses of Neutron logging instruments have been determined opposite formations of different porosities and under various borehole conditions. The results of these tests are presented in several charts which show how the Neutron log is affected by the following factors: hole diameter, casing, cement, salinity and weight of drilling mud, and position of logging tool with respect to the wall of the hole. The responses in the case of empty holes are also shown. A chart is furthermore presented which shows the shapes of the Neutron log, as a function of logging speed and time constant, at the boundaries between two formations with different porosities. These were derived mathematically using as a basis laboratory determination of the shape of the curve under static conditions, i.e. at very low logging speed. Corrections for the readings made opposite thin beds are given by these computations. The correction is found negligible under usual logging conditions for beds thicker than about 4 ft. INTRODUCTION The Neutron log is used in borehole surveys both for the delineation of porous formations and for the quantitative estimation of their porosities.1,2,3,4,5 It is common practice to calibrate the response of the Neutron log in terms of porosity values for each given geological unit by means of empirical comparisons between the deflections of the neutron curve and the porosity values given by the core analysis in a sufficient number of wells. Usually, the plots of the porosity values vs Neutron log deflections show a definite trend. It is therefore possible to trace an average line across the plotted points. This average line constitutes a calibration curve which can be used to evaluate the porosities from the Neutron logs in the other wells drilled in the same region. Futhermore, when the porosity values are plotted on a logarithmic scale and the Neutron log deflections on a linear scale, the calibration curve is practically a straight line. Accordingly the calibration curves are often determined by simply tracing a straight line between two points corresponding to two widely different porosities. Different choices are made for these two points, depending on local conditions. For example, one point will be defined by plotting the deflection of the Neutron curve opposite a formation known to be very tight, for which an average porosity value of 1 or 2 per cent is assumed. The other point may correspond to shale sections, to which a porosity of around 40 per cent is ascribed. The information provided by the eletrical logs — in particular the Laterolog, Limestone log or Micro-Latero-log — is also very often a help in the calibration of the Neutron logs. Empirical approaches such as these make possible the derivation of fairly reliable porosity values from the Neutron logs in many cases, at least in open holes and in essentially clean formations. There are, however, several causes of uncertainty which may sometimes entail appreciable errors. On the one hand, the Neutron log readings are influenced by the borehole conditions: hole diameter, presence or absence of casing and cement, presence or absence of drilling mud, characteristics of the mud, and position of the logging instrument with respect to the wall of the hole. The amplitudes of the curves opposite thin beds are furthermore atfected by the bed thickness,

Jan 1, 1957