Search Documents

By Thomas E. Leontis

INTRODUCTION THE importance of magnesium alloys in the manufacture of aircraft engines has been realized for many years. A concentrated effort has been exerted in the laboratories of the Dow Chemical Co. to develop magnesium-base alloys with improved properties at elevated temperatures whereby greater advantage can be taken of the inherent lightness of these materials. In an earlier publication,1 attention was called to the superior tensile properties and resistance to creep of cerium-containing magnesium alloys at temperatures up to 700°F. More recently, additional data on magnesium-cerium alloys have been furnished by Murphy and Payne.2 The present paper deals with the mechanical properties of sand-cast magnesium alloys containing zinc, at temperatures up to 500°F. The study includes binary Mg-Zn† alloys containing up to 10 pct zinc and several ternary and some polynary alloys based on the Mg-1Zn,†Mg-3Zn, Mg-4.4Zn, Mg-6Zn, and Mg-10Zn binaries. The compositional variation in the tensile properties, hardness, and creep at room and elevated temperatures, and in the electrical conductivity at room temperature has been determined. The results of these tests show that many zinc-containing magnesium alloys exhibit resistance to creep at elevated temperatures significantly higher than that of present commercial magnesium alloys, but lower than that of alloys of the magnesium-cerium type. In addition, they have high tensile properties at room and elevated temperatures and high conductivity. This combination of mechanical properties and conductivity indicates that these alloys should be given serious consideration for commercial applications involving exposure to temperatures higher than those to which present commercial magnesium alloys can be taken safely. LITERATURE The properties of sand-cast magnesium alloys containing zinc as a principal alloying element have not been investigated very extensively, especially at elevated temperatures. The following remarks, which are confined to sand-cast alloys, will serve as a summary of the most important references on this phase of magnesium metallurgy. The first recorded determination of the tensile strength of binary Mg-Zn alloys as a function of zinc content was reported by Aitchison.3 Similar studies, including the measurement of elongation and hardness, have been performed by Gann and Winston,4 Dumas and Rockaert,5 Haughton and Prytherch,6 and by Spitaler, the last being reported by Beck.7 A slight superiority in the tensile strength of chillcast Mg + 8 Zn alloy over the sand-cast alloy was noted by Maybrey 8 That alloys of magnesium containing 5 to 12 pct zinc

Jan 1, 1948

By T. E. Leontis

The importance of magnesium alloys in the manufacture of aircraft engines has been realized for many years. A concentrated effort has been exerted in the laboratories of the Dow Chemical Co. to develop magnesium-base alloys with improved properties at elevated temperatures whereby greater advantage can be taken of the inherent lightness of these materials. In an earlier publication, attention was called to the superior tensile properties and resistance to creep of cerium-containing magnesium alloys at temperatures up to 700°F. More recently, additional data on magnesium-cerium alloys have been furnished by Murphy and Payne. The present paper deals with the mechanical properties of sand-cast magnesium alloys containing zinc, at temperatures up to 500°F. The study includes binary Mg-Znt alloys containing up to 10 pct zinc and several ternary and some polynary alloys based on the Mg-~Zn,f Mg-jZn, Mg-4.4211, Mg-6Zn, and Mg-roZn binaries. The compositional variation in the tensile properties, hardness, and creep at room and elevated temperatures, and in the electrical conductivity at room temperature has been determined. The results of these tests show that many zinc-containing magnesium alloys exhibit resistance to creep at elevated temperatures significantly higher than that of present commercial magnesium alloys, but lower than that of alloys of the magnesium-cerium type. In addition, they have high tensile properties at room and elevated temperatures and high conductivity. This combination of mechanical properties and conductivity indicates that these alloys should be given serious consideration for commercial applications involving exposure to temperatures higher than those to which present commercial magnesium alloys can be taken safely. Literature The properties of sand-cast magnesium alloys containing zinc as a principal alloying element have not been investigated very extensively, especially at elevated temperatures. The following remarks, which are confined to sand-cast alloys, will serve as a summary of the most important references on this phase of magnesium metallurgy. The first recorded determination of the tensile strength of binary Mg-Zn alloys as a function of zinc content was reported by Aitchison. Similar studies, including the measurement of elongation and hardness, have been performed by Gann and Winston,' Dumas and Rockaert, Haugh-ton and Prytherch,6 and by Spitaler, the last being reported by Beck.' A slight superiority in the tensile strength of chill-cent Mg + 8 es alloy Over the sand-cast alloy was noted by Maybrey.8 That alloys of magnesium containing 5 to 12 pct zinc

Jan 1, 1949

By Norman D. Fitzgerald

IN 1943 the petroleum industry completed a series of practical adjustments to the acute problems which dominated the scene a year earlier. The crisis in petroleum transportation from the Gulf Coast to the East Coast was met by the completion of overland pipe lines supplementing emergency haulage by tank car so pressure on consumers along the Atlantic Seaboard was appreciably relieved. Later in the year when the western Atlantic was largely cleared of submarines, the sharp reduction in the hazards of marine transportation permitted the resumption of coastwise traffic and imports from South America. Nationwide restrictions in the use of gasoline and fuel oils became necessary as military demands for all petroleum products mounted to high levels.

Jan 1, 1944

EDITORIAL comments on the anthracite report of the Federal Fact-finding Coal Commission, which became public on July 5, together with an analysis of its more important conclusions, will be found on another page of this issue. In this place, only a few extracts from the report, bearing more directly on technical matters, can be quoted, for lack of space. COST OF MINING Mining cost, as it stands on the books of each mining company, represents the average cost of the total output, all sizes, of anthracite. Egg coal has at least five times the market value of barley, but these' sizes are mined together and their costs can not be separated. Mine costs directly reflect the conditions under which these deposits of coal are recovered. Even within the few counties in which anthracite is found there is a conspicuous range of natural conditions. The distinc-tion between the Northern, Middle, and Southern field, or, as they are also termed, the Wyoming, Lehigh, and Schuykill regions, is primarily geologic and topo-graphic, but the effects of the natural conditions largely control costs. The contrast is great between Some of the level-lying beds of moderate but fairly constant thickness under the broad Wyoming Valley, where mining and underground haulage present relatively simple problems to the engineer, and the steeply pitching or overturned and faulted beds of variable thickness in the Schuykill field, where crushed coal' and treacherous roof multiply the difficulties of mining; and increase the unavoidable waste. Even more direct is the connection between geologic processes and the, differences in the character of the coal as mined, the varying proportions of large and small sizes demanding differences in preparation and resulting in different average prices realized for the product of the mines.

Jan 8, 1923

By AIME AIME

DURING the morning session," on Feb. 17, papers were presented and discussed regarding a recent wire saw installation, cement rock quarry operations, hydration factors in gypsum deposits and the status of the phosphate industry of the West. Oliver Bolvles presided and there were about twenty-five members present. W. M. Weigel's paper (T. P. 262), "The Application of the Wire Saw in Marble Quarrying," was read by the author. He described the recent installation of the St. Clair Marble Co., near Guion, Ark. Since the use of the wire saw for quarrying is comparatively new and the fact that it has been almost entirely limited to slate quarries heretofore, ?he description and data given in this paper were of much interest.

Jan 1, 1930

By AIME AIME

MODERN metallurgy is an art and a science. The art is process metallurgy-extracting metals from their ores, refining them, and alloying them with one another and with certain nonmetals to produce thereby a variety of metallic materials which, owing to a wide range of useful properties, are for many purposes more valuable to man than the individual metals themselves; process metallurgy also includes shaping or otherwise treating metals and alloys to form objects useful to a complex industrial world. The science is physical metallurgy-organized knowledge of the constitution and internal structure of metals and alloys, of the relation of their composition and structure to properties, and of the laws, theories, and hypotheses that purport to explain this relation.

Jan 1, 1942

By M. M. Leighton

THE engineers of Illinois have been submitting to the State Geological Survey an increasing number of requests for advice on their geological problems, including landslides, unequal settling of fills, laying pavements across peat bogs, shattering and heaving of pavement by frost action, etc. The authors discussed the behavior of landslides, their effects, their causes, a tentative classification, and remedial measures. In the latter connection the efficacy of drainage and how it should be handled in order to be most effective was considered. The principles and efficacy of other remedial measures, such as subsurface blasting, rock anchoring, installation of wood, concrete or steel piling, construction of retaining walls, construction of cribbing and reduction of slope were also discussed. Attention was also given to the matter of applying geological knowledge to avoid undesirable highway locations, and a specific example was cited.

Jan 1, 1929

By J. L. Tomlinson, B. D. Lichter

Electrical resistivities 01 liquid Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi alloys were measured using an electrodeless technique. The resistivities ranged from 50 to 160 microhm -cm, temperature dependences were positive, and no sharp peaks in the composition dependence of the resistivity were observed. On the basis of these observations, it was concluded that the alloys are typical metallic liquids. The electron con-cent9,ation was calculated from the measured resis-tizlity and available thermodynamic data using a model which attributes electrical resistivity to scattering by density and composition flzcctuations. A correla-tion was shown between the departure of the electron concentration from a linear combination of the pure component valences and the value of the excess integral molar free energy. Calculation of the temperature dependence of the electrical resistivity showed a need for more detailed thermodynamic data in these systems and led to suggestions for improvement in the concept of residual resistivity in the fluctuation scattering model. THE electrical resistivity of liquid metals provides information regarding interatomic interactions and their effects upon structure. In this experiment an electrodeless technique was used to measure the electrical resistivities of liquid alloys of Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi, and the results were used with thermodynamic data to calculate a parameter which reflects the tendency toward localization of electrons due to compositional ordering. It was found that the resistivities of these alloys are generally metallic in magnitude and temperature dependence. The electrical and thermodynamic properties are discussed in terms of the fluctuation scattering model'22 which supposes that the electrical resistivity arises from scattering due to a static average structure and departures from the average due to fluctuations in density and composition. Further, this model is compared with the pseudopotential scattering model of Ziman et al.3-5 EXPERIMENTAL PROCEDURES Alloy samples were prepared from 99.999 pct pure elements obtained from American Smelting and Refining Company (except tin which was obtained from Consolidated Smelting and Refining Company.) J. L. TOMLINSON, Member AIME, formerly Research Assistant Division of Metallurgical Engineering, University of Washington, Seattle, Wash., is now Physicist, Naval Weapons Center, Corona Laboratories, Corona, Calif. 0. D. LICHTER, Member AIME, is Associate Professor of Materials Science, Department of Materials Science and Engineering, Vanderbilt University, Nashville, Tenn. This work is based on a portion of a thesis submitted by J. L. TOMLINSON to the University of Washington in partial fulfillment of the requirements for the Ph.D. in Metallurgy, 1967. Manuscript submitted May 31, 1968. EMD Weighed portions were sealed inside evacuated silica capsules, melted, and homogenized before the resistivity was measured. The resistivity of a liquid alloy was measured by placing the sample inside a solenoid and noting the change in Q. According to the method of Nyburg and ~ur~ess,~ the resistivity of a cylindrical sample may be determined from the change in resistance of a solenoid measured with a Q meter as T7--5--W =R7JT^ ='Kc-lm(Y) [1] where L, R, and Q = wL/R are the inductance, series resistance, and Q of the solenoid. The subscript s refers to the solenoid with the sample inside; the subscript 0 refers to the empty solenoid. Kc is the ratio of the sample volume to coil volume and y = 2 [bei'0(br)-j ber'o(br)~\ br\_bero(br) +j bei0 (br) expressed with Kelvin functions which are the real and imaginary parts of Bessel functions of the first kind with arguments multiplied by (j)3'2. The argument of the function Y is hr where r is the sample radius and b2 = po~/p, i.e., the permeability of free space times 271 times the frequency divided by the resistivity in rationalized MKS units. Since Eq. [I] cannot be solved explicitly for p, values of Kc. lm(Y) were tabulated at increments of 0.1 in the argument by. A measurement of Q, and Q, determined a value of Kc . lm (Y) and the corresponding value of br could be read from the table. From the known r, uo,, and w, the resistivity, p, was determined. The change in Q was measured after letting the encapsulated Sample reach equilibrium inside a copper wire solenoid. The solenoid was contained in an evacuated vycor tube in order to retard oxidation of the copper while operating at high temperatures and heated inside a 5-sec-tion nichrome tube furnace capable of obtaining 900°C. Temperature was determined with two chromel-alumel thermocouples, one in contact with the solenoid 30 mm above the top of the sample and the other inserted in an axial well at the other end of the solenoid and secured with cement so that the junction was 2 mm below the bottom of the sample. Temperature readings were taken with respect to an ice water bath junction, and the voltage could be estimated to the nearest thousandth of a millivolt. The lower thermocouple was calibrated by observing its voltage and the Q of the coil as the temperature passed through the melting points of samples of indium and tellurium. The upper thermocouple reading was systematically different from the lower thermocouple reflecting the temperature difference due to a displacement of 60 mm axially and 6 mm radially. Calculations show that the gradient over the sample was less than 2 deg. Q was measured by reading a voltage related to Q from a Boonton 260A Q meter with a Hewlett Packard

Jan 1, 1970

By AIME AIME

ANDREW FLETCHER, newly elected Treasurer and Director, has spent his entire mining career in the employ of the St. Joseph Lead Co. and brings to the Institute Board a career rich in financial experience and varied in interest and accomplishment. "Drew" Fletcher was born in New York City on Feb. 6, 1895. After graduating from the Sheffield Scientific School of Yale in 1916 as a mechanical engineer, he became a shipyard mechanic in Wilmington, Del. The next thirteen years saw. him gradually enlarging his responsibilities until he ultimately became the head of the W. & A. Fletcher Co., in Hoboken, N. J., ship repairers. In 1929 his program for merging the Fletcher plant with five other New York shipyards was finally consummated in the formation of the United Dry Docks, Inc., which subsequently was purchased by Bethlehem Steel, with the result that today the old Fletcher yard and organization has been expanded into one of the finest ship repair units in the United States.

Jan 1, 1944

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964

By R. K. Govila, E. H. Parkison

THE interplanar angles for hcp metals vary with c/a ratio, and therefore must be computed separately for each particular metal or alloy. Manual computation of these angles is laborious and time consuming, and for this reason computer programs have been developed to accomplish this task.1"3 However, these programs have certain disadvantages. For example, they require prior knowledge and understanding of ALGOL or FORTRAN languages. Further, they will not print out specific angles but instead give all angles between given limits—thus program2 prints out a total of 26,649 angles between planes with indices and in the range from (4 4 4) to (4 4 4) for any given c/a ratio. The purpose of this note is to present a simple and inexpensive computer program for accomplishing this task. This program is written in BASIC language4 which does not require any prior knowledge of computer programming, and is ideally suited for nonprofessional programmers. It also provides flexibility for the user by allowing him to select any indices for as many or few planes as desired for any given c/a ratio. The computer program proposed below is based on the relationship in which + is the angle between any two planes and . TO illustrate use of the program, consider the problem of calculating the interplanar an-

Jan 1, 1970

By Erwin Pink

It has been pointed out in a previous publication' that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e' the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E' is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson's ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By J. M. Campbell, T. S. Buxton

The most widely used methods of predicting the volumetric properties of gas are based on the principle of corresponding states, which asserts that the compressibility factor is a universal function of reduced temperature and pressure. Previous studies have shown that the acentric factor, as proposed by Pitzer, l is an important addition to reduced pressure and reduced temperature as factors affecting the compressibility factor. Results of this study indicate that, if the pseudocritical temperature and pressure used to determine the reduced conditions are adequately predicted, characterization of natural gas-carbon dioxide mixtures with the acentric factor will allow reliable determination of the compressibility factor. Comparisons of predicted and experimental compressibility factors have shown that the pseudo-critical constant rules of Stewart, Burkhardt and Voo 2 are satisfactory for hydrocarbon mixtures. However, these rules fail to predict the pseduo-critical constants for hydrocarbon-carbon dioxide mixtures. Based on graphically determined pseudocritical temperatures for binary hydrocarbon-carbon dioxide mixtures, a correlation which gives the required correction to the Stewart, Burkhardt and Voo rules was prepared and a compressibility factor prediction technique was proposed. To test the proposed technique, compressibility factors for live mixtures of methane, carbon dioxide and either ethne or propane were experimentally determined at 100, 130 and 160F and pressures up to 7,026 psia. The predicted and experimental compressibility factors for these live mixtures had an average absolute deviation of 0.55 percent. INTRODUCTION Two-parameter generalized correlations based on the principle of corresponding states (PCS) are presently available for reliably predicting the compressibility factor of lean natural gas, i.e., natural gas with low concentrations of hydrocarbons heavier than methane. When these same correlations are used for mixtures of natural gas and carbon dioxide, large deviations between actual and predicted compressibility factors are observed. This study was undertaken to provide a means for accurately predicting the compressibility factor for such mixtures. In the past, two avenues of approach have been employed to extend the applicability of the PCS. The first has been to introduce additional parameters. The second has been to develop combination rules for predicting pseudocritical constants which do not suffer from the limitations of the commonly used molal average constants. In this study, both of these approaches have been considered and employed to arrive at a method for predicting the compressibility factor of mixtures of hydrocarbons and carbon dioxide. SELECTION OF A THIRD PARAMETER Failure of the original PCS to predict the compressibility factor for all pure gases, regardless of their mass, shape or polar moment, has led to the introduction of additional parameters into the PCS. Parameters have been introduced to correct for quantum deviations,3-5 non-spherical or globular shapes6-9 and for polar moments.8-12 In addition to these parameters which are based on some microscopic property and intended to correct for some specific cause of deviation, more general parameters based on some bulk property have also been introduced.1913-16 To use additional parameters to correct for each of the possible causes of deviation among the individual constituents of a gas mixture would require a rather complex form of the PCS. To maintain the PCS in as simple a form as possible, it is more desirable to have a single third parameter which is based on some bulk property influenced by several of the factors causing deviations. The third parameter selected for use in this study is a factor originally proposed by Pitzer.9

By T. L. Joseph

A DEMAND for specialized knowledge has directed engineering curricula towards competency in some particular field or occupation. Preparation for life in a broad sense of completeness has received little consideration. Ways and means are needed for weaving some of the threads of liberal education into the fabric of engineering education. Any effort to develop a humanistic-social stem of engineering education will depend largely upon the content of the courses and the type of instruction offered. Many of the courses in college curricula are intended to lay a foundation for more advanced courses to be taken later by those. who specialize in some particular field. Students in other fields lack the background necessary to take the advanced courses and have too much detailed information, soon forgotten, forced upon them if they pursue the foundation courses. To develop a humanistic-social stem for engineering education existing catalogue courses selected should follow some general plan aimed towards broad educational objectives. Courses packed with detailed factual information are necessary for the stu-

Jan 1, 1947

By A. C. Emery

The physical and chemical properties for the metalliferrous feed materials to the Imperial Smelting Process blast furnace are defined and the means of achieving these properties by the sintering or briquetting routes discussed. Modern sinter plant performance data is included with a plant flow sheet showing draughting patterns. The necessity for ensuring an adequate SO2 content in sinter machine gases when roasting sulphide materials to enable conversion to sulphuric acid in a contact acid plant is described. The ability of the process to consume limited quantities of oxide materials, residues from other processes and other secondary sources is discussed. The argument for a briquetting route is developed out of this limitation and the merits of cold and hot briquetting examined. Development work on the hot briquetting route for this purpose is briefly described and several flow sheets outlining possible applications for hot briquetting to different raw material situations including the preparation of low lead charges for the furnace are presented.

Jan 1, 1977

By E. D. Glass, R. C. Hessing

The volume of gas in storage reservoirs may be compuled from estimates of hydrocarbon pore volume and gas density. However, both are dificult 10 estimate accurrately. Further, no adequate method has been presented for estimating reservoir performance during operation for Volumetric gas-storage reservoirs. Normally, gas-storage reservoirs exhibit small pressure gradients in the area conr(zilliitg the storage wells, even under conditions of maximum injection or withdrawal. A zone of low permeability usally surrounds, and is in communication with, tile permeable zone which causes the storage reservoir to exhibit a definite pressure lag, as evidenced by lack of pressure stabilization after extended periods of shut-in. An analysis is presented for determining pore volume and gas in place, and for predicting future reservoir behavior of such reservoirs. The mathematical development is presented and a solution is shown for an operating storage reservoir. INTRODUCTION Depleted gas reservoirs arc often used for gas storage. The reservoir usually contains a permeable area in which numerous storage wells arc located. The permeable zone permits high deliverability and injectivity with relatively small pressure loss. However, pressure equilibrium may not be attained even after long periods of shut-in because of the fact that the permeable zone is in communication with an adjacent tight section. Most of these gas-storage reservoirs are sand lenses, such as ancient beaches or offshore bars. The areal geometry of these reservoirs is normally such that flow in the tight zone will be approximately linear, and the solutions presented here should apply. DISCUSSION For purposes of this paper, a gas-storage reservoir is considered to consist of a volume of permeable rock in communication with tight rock, all of which is surrounded by an impermeable barrier. Pressure gradients across the permeable zone are small due to low flow resistance and well density. Hence, the permeable zone is considered to be at a uniform pressure which is only a function of time as gas is injected or withdrawn. The tight zone is considered to be linear with uniform permeability and porosity, and the pressure in the tight zone is a function of both position and time. l'wo solutions for flow in this system are used to define the reservoir and determine its properties. The first solution is for an infinite linear tight zone in communication with the permeable zone. The expression for constant gas-withdrawal rate is Eqs. I and 2 ore superposed to account for varying rates of production or injection and are used to fit gas-storage field reservoir history. The solution for the infinite case, Eq. 1, is first applied to field data for early times following a shut-in period. Constants BDa and c are ohtained by a least-squares fit of pressure and rate data. After the pressure wave from gas injection or withdrawal reaches the external boundary of the tight zone, the infinite solution will no longer apply and pressure behavior should be more nearly represented by Eq. 2 for a gas reservoir in communication with a finite linear tight zone. The values of the constants found from curve-fitting Eq. 1 to the early time data may then be used in Eq. 2 that only the coefficient- L containing the unknown

By J. B. Conway

RECENT studies of first-stage creep data have led to a special least-squares procedure for use in calculating the Andrade creep-equation constants. This procedure is easy to apply, uses only experimental data, and yields results which do not vary with the individual making the analysis. Taking logarithms of the Andrade equation I = lo(1 +ßl1/3)ekt leads to In l = In lo + In(1 + ßl1/3) + kt A residual can then be defined as the difference between the logarithm of an experimental length value and the logarithm of a calculated length value. Following the usual least-squares approach differentiation with respect to 10 and k of the expression for the sum of the squares of the residuals leads to two equations which cannot be solved directly for the three constants involved. However, values of ß can be assumed and corresponding values of lo and k can then be calculated. Then the sum of the squares of the residuals can be calculated. For a certain value of ß this sum will exhibit a minimum value to identify the least-squares values for ß, lo, and k. An illustration of the application of the above least-squares approach is obtained by employing the creep data for lead originally presented by Andrade' in the development of the one-third creep law. A plot of the sum of the squares of the residuals as a function of ß is shown in Fig. 1 along with the corresponding lo and k values. The minimum is seen to occur at ß = 0.0143 from which lo = 39.149 and k = 7.27 x 10-5. Based on these results the Andrade equation for these lead data is 1 = 39.149(1 + 0.0143 t1/3)e7.27 x 10-5t compared to the equation I = 39.13(1 + 0.01457/l/3)e6.95 X 10-5t developed by Andrade (calculation procedure not given but was probably a graphical solution). Calculating length values using the above equations and comparing with the experimental length values, residuals corresponding to the difference between experimental and calculated length values can be obtained. The sum of the squares of the residuals can then be calculated. For the case of the least-squares approach a value for this sum was found to be 2.37 x 10-3 compared to a value of 3.47 x 10" for the equation originally proposed by Andrade. In other words, while the constants proposed by Andrade provide an excellent fit for the lead data, a still better representation is afforded by applying the least-squares approach discussed above. A similar result was obtained for the lead data at 162oc.l The least-squares approach led to 1 = 9.866(1 + 0.0497 t1/3)el.011 x 10-2t compared to the equation I = 9.94(1 + 0.0433 l1/3)e1.06 X 10-2t given by Andrade. In this case, too, the sum of the squares of the residuals is slightly smaller for the equation based on the least-squares approach. It should be pointed out that a double trial and er-

Jan 1, 1965

By R. F. Krueger, L. C. Vogel

A design is presented for an electrical analog computer which can solve non-steady state heat transfer problems in an extensive radial forrnation containing a moving cylindrical source. The computer is used to simulate a .simplified thermal oil recovery process in which heat transfer from a moving, constant temperature source takes place radially by conduction only. Temperature distribution curves are .shown for several different assumed modes of travel for the heat source. The data are used to estimate the residual fuel requirements necessary to maintain a self-propagating isotherma1 front for the particular system being studied. Although the computer is designed to represent an unique system. conversion factors can he adjusted to show the effects of changing the assumed values of system constants, such as thermal conductivity of the formation and temperature of the source isotherm. Examples are given to illustrate the relative influence the assumed values of these variab1es will have upon the quantity of fuel required to maintain the source. The maximum effect of heat transfer by the flowing air stream is estimated mathematically, and full requirements for this system are shown to he markedly reduced. Inasmuch as the examples discussrd refer to a simplified process, the results are not directly applicable to a practical field operation. It is believed, however, that the data il1ustr-ate some general trends which are important in thermal recovery processes. Data from laboratory and field experimentation can he used to modify the computer to take into account the influence of heat transfer by various mechanisms, for example, by injected air and by fluids ahead of the hot zone. With .such refinements it would be possible to estimate more accurately the limiting values for the rate of travel of the high temperature front and for the required air- injection rates. Use of this computer should aid in evaluating the economic feasibility of oil recovery by various thermal processes. It is hoped this paper will stimulate further work by others to help accomplish this objective. As the costs of exploration for and development of new oil fields rise. increasing the recovery of oil from established fields becomes more and more important. In fields containing low gravity crude oil, ultimate recoveries by primary means are sometimes less than 10 per cent and often total only 10 to 20 per cent of the oil in place. Conventional secondary recovery methods are not always effective in increasing this total. Methods which have been proposed for increasing the recovery of viscous oils include thermal processes for increasing the mobility of the oil. One method is to provide a moving heat source generated within the formation to heat the oil and a flowing gaseous medium (for example, air) to sweep the oil to the producing wells. The possibility of such a process has intrigued engineers for many years.'. '." but little or no information has been available in the literature relative to the technical or economic feasibility of this method. Recently, however, interest has been revived by publication of laboratory and field test results indicating the feasibility of maintaining

Jan 1, 1956

By P. G. Shewmon

A novel technique for determining the surface energy (?) and its derivative with respect to orientation, (?') is described. Essentially it involves the 'floating" of a wedge on the substrate, said wedge being made of a material which is not wet or only slightly wet by the substrate, i. e., as a greased needle "floats" on water. A thermodynamic analysis of a system in which the wedge is supported entirely by surface energy is given. If the original suyface is not at a cusp orientation, the surface tension is directly measurable from the groove angle formed. If the original surface is at a cusp orientation, there may or may not be a groove depending on the relative value of ?' and the weight of the wedge. Experiments primarily on copper and silver showed that sapphire, quartz and refractory metal wedges were wet while graphite wedges were not. The technique was demonstrated to work using graphite wedges, but the results obtained were not as eccurate as those obtained by other workers using the wire-creep experiments. It is concluded that the technique might prove most useful with non-metals where ?' is large and filament creep experiments would be quite difficult. If an absolute value of the surface free energy (?) of a metal is to be determined, the most reliable methods used to date measure an average over the various orientations exposed on a polycrystalline sample. For example, ? for silver, gold, and copper have been measured by determining the force required to just keep a thin wire,' or foil,' specimen from contracting under the influence of ?. Herring 3 has predicted and experiment confirms, that the sensitivity of this method is inversely proportional to the grain size.' Thus it cannot be used to measure ? for a particular orientation by using a foil single crystal or a very coarse-grained specimen. An accurate value if ? for tungsten averaged over a range of orientations has been determined using a field emission technique. The same techniques cannot or have not been used to measure ? for non-metallic solids, and as a result the values available are much less accurate.4 This Paper resents a means of making an absolute determination of ? for a particular surface orientation on any solid, as long as the given surface orientation does not break up into other orientations during an anneal. Experimentally ? is found to vary with orientation and at a few low index orientations it is found to have a cusped minimum, i.e., the derivative of ? with respect to the orientation of the surface changes discontinuously at the low index orientation, see Fig. 1. The slope of a plot of ? vs orientation (herein designated ?') is called the torque on the surface, since it tends to rotate the exposed surface toward the low index orientation, or if the surface is at the cusp orientation it opposes any force tending to rotate the surface out of the low index orientation. The ratio ?'/? has been determined for a few metals, but in cases where this ratio is high there is presently no means of determining either ?'/? or the absolute value of ?' for the orientations present on an annealed surface. The technique discussed herein also provides a means of determining an absolute value of ?' for those orientations which deviate only infinitesimally from a cusp orientation. It should work best on surfaces where ?'/? is large; that is, for cases where no other technique is available for measuring ?'. Aside from trying to learn more about surfaces through measuring ? and ?', the primary reason for wanting values of ? or ?' is to study adsorption. From measurements of the variation of ? for a particular orientation with the concentration of an impurity, one can obtain the number of impurity atoms adsorbed per unit area (Ti) on that orientation using the Gibbs adsorption equation.' where µi is the chemical potential of the adsorbed impurity. Thus, if absolute values of ? could be obtained for the free surface of a given surface orientation as a function of µi, ri could be determined for the given orientation. Furthermore, by equilibrating a grain boundary with the given surface at various values of ki, one could also determine ri for the grain boundary. Similarly Robertson 6 has pointed out that if y is taken to be a continuous function of and µi, then a2 ?/a @a µ2 = a2 ?/a pi a +. Thus, at all orientations away from cusps the following equation holds From a measurement of ?' vs ki, it is thus possible

Jan 1, 1963

By Robert W. Elayer

In August 1973, Fluor Utah, Inc. was awarded a contract by the Office of Coal Research (now part of the Energy Research and Development Administration), Department of the Interior, for the examination of the unique problems of large-scale surface coal mining to supply coal conversion complexes. The project consists of two phases: (I) data base development and organization and the formulation of a mathematical computer modeling system for surface mining; and (II) computer manipulation of the data base in accordance with the model to formulate several typical preliminary mine and preparation plant designs. Phase I is scheduled for completion by the end of July 1975 and Phase II is scheduled to be complete by the end of January 1977. This paper briefly discusses the effort for only one aspect of this project-the foundation for geologic modeling developed in Phase I. The Phase I task of geologic modeling can be broken down into two subtasks: (1) identify areas containing sufficient resources of surface-minable coal to support at least one large-scale mining complex, and (2) characterize the coal deposits in these areas for computer storage and retrieval. Identification of Resource Regions The basic production design criteria for large-scale surface mining, as stated in the contract, is the production of 75,000 tpd, or more, of bituminous coal. Based on a constant total Btu delivered to the preparation plant, daily production requirements for the different coals are as follows: Bituminous Coal 75,000 tons Subbituminous Coal 99,500 tons Lignite 143,500 tons Although surface mining on this scale is presently non-existent, it is deemed that future operations, in order to meet the increased energy demands, will have to look forward to much larger scale mining complexes. These tonnage requirements are meant to be used only for the delineation of general areas suitable for large-scale surface mining, termed "Strippable Coal Resource Regions." They were determined largely from the latest complete detailed coal resource estimates of the U.S. Bureau of Mines. Nine strippable coal resource regions, containing over 100 billion tons of strippable coal resources, were identified [(see Fig. 1)]. The delineation of these regions was based entirely upon estimates of surface-minable coal resources and the production design criteria for large-scale surface mining. If surface-mined coal was combined with underground production, or if smaller production rates were specified, then other areas which were omitted here would be included in the regions. Changing the outline of the regions, however, would not add any new mining situations to be studied in Phase II. Characterization of Coal Deposits The second subtask involved the general characterization of the coal deposits contained in the strippable coal resource regions. The geological information gathered

Jan 1, 1976