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By Michael B. Gross

A numerical study of the vulnerability of unlined tunnels in jointed rock has been performed with the STEALTH computer program, using the CAVS model for jointed rock. CAVS, for Cracking And Void Strain, is a constitutive model that can simulate the initiation/propagation of fractures and the slip along fracture planes in a jointed rock mass. The CAVS model is unique because it represents a spatially oriented approach to rock failure, rather than the traditional invariant formulation, and because the CAVS submodels for slip friction and slip-induced dilatancy are used to represent the weakening influence of joints, rather than applying ad hoc modifications to the elastic moduli of the host rock. The CAVS model, as embedded in the STEALTH computer program, has performed numerical simulations of tunnel collapse at high overstress levels. These calculations show that the ultimate strength of the tunnel depends strongly on the joint properties, and that the results of the calculations are in qualitative agreement with the observed data for collapse of a tunnel in tuff.

Jan 1, 1984

By J. E. Russell, Y. J. Wang

In this paper, we report the results of a study of the characteristics of Texas lignite based on a proximate analysis data base previously published by the Bureau of Economic Geology, University of Texas at Austin and the U.S. Bureau of Mines. The original impetus for this study was the desire to perform a parameter study in connection with the siting of potential underground gasification tests in Texas. A numerical model of the gasification process was available and required proximate analysis data, among other parameters, as input. If proximate data were available for a particular site, a prediction of the product gas quality could be made. However, in preliminary siting studies, it would be advantageous to know what the desirable characteristics of the lignite are, in order to target general areas for drilling. Consequently, a parameter study was in order. This paper presents the methodology required to systematically vary proximate analysis parameters and estimate the corresponding energy content for various group(or formation)-facies classifications of Texas lignite.

Jan 1, 1983

By Lyall Zickrick

EXPERIMENTS of previous investigations have indicated that calcium-copper alloy, when used as a deoxidizer for molten copper, results in a sound copper casting of good physical and electrical properties. Bradenberg and Wiens1 have obtained successful results in casting sound copper using calcium for deoxidizing. Masing2 has obtained deoxidized copper of high density and high conductivity by use of calcium. Pratt,3 in 1907, patented the use of calcium for the deoxidation and degasification of, copper. Schumacher, Ellis and Eckel 4 in 1929, conducted a series of experiments on deoxidizing copper with calcium. They concluded that so long as there is only a small percentage of residual calcium the mechanical and electrical properties of the copper deoxidized are not impaired; and the deoxidation is thorough. For this investigation, a, copper-calcium alloy high in calcium and 10 variously deoxidized copper ingots were prepared. The investigation concerns itself with the casting properties and structure of these variously deoxidized ingots, their working and annealing characteristics, and the resulting physical and electrical properties of the worked materials.

Jan 1, 1932

By S. H. Cathcart

Price, production and drilling operations exceeded any year since 1930. A top price for crude of $2.55 was maintained from May 1 to November 6 and increased activity about coincides with that period. The average crude price for the year was: Bradford, $2.46; Kane-Butler, $2.34; Southwest Pennsylvania, $2.13. Production for the year exceeded 15 million barrels, an increase of about 2 million barrels over 1933. That this increase was more than justified by market demand is indicated by a reduction of 892,000 bbl. in stocks for the year. Two classes of data appear on Table 1, which are differentiated by footnote references. Where possible the .figures were obtained from individuals and companies that, from long acquaintance and varied contacts, are most capable of supplying an estimate where an estimate is necessary. The remaining data represent a rather careful compilation from all available published records (see p. 378). Drilling operations and production as summarized by the Oil City Derrick are as shown on Table 2.

Jan 1, 1935

By Max Barber

PRESENT equipment and practices in open-pit mines of the Lake Superior iron ranges have been described recently in some detail by A. H. Hubbell.1 It is anticipated that any further improvements will be the result of gradual evolution of present methods and equipment, just as those now used have been gradually evolved from earlier methods. An exception to the process of gradual evolution during the last decade has been the adoption of electric power for operating shovels and trains in open-pit mines, but it is not expected that any such revolutionary changes will be made in the future. The use of Diesel, engine equipment will gain considerable headway, no doubt, and will find favor in certain lines of operation as improvements and adaptations are evolved to meet particular requirements. The question of installing belt conveyors for handling material from deep mines of restricted area, where haulage grades become a serious consideration, or even for transferring earth, rock, or ore material for distances of several miles, is now being studied and some very interesting data are being obtained.

Jan 1, 1932

By D. A. Rice, R. L. Stone

Studies of the possible effect of plant water chemistry on the strength of unfired iron ore pellets apparently have not been reported in the literature. Naturally occurring soluble salts were removed from magnetic concentrate filter cakes obtained from several iron ore concentrators. Laboratory balling tests showed that unfired pellets made from these "clean" filter cakes were 50-100% stronger than the usual unfired pellets containing the salts. The fact that certain chemical additives dissolved in the water used for balling "clean" concentrates decreased the strength of unfired pellets indicates that salts in the plant process water may be responsible for lower strengths. According to chemical analyses of plant process waters at these plants, calcium and magnesium are probably the most detrimental salts in the plant circuits. It is suggested that calcium, magnesium, and other polyvalent cations in the mill process waters ion-exchange for lower-valence cations in the bentonite and thereby destroy the electrostatic-charge bonding in the green pellet. Some practical guidelines are also included for plant balling practices.

Jan 1, 1973

By G. Herget

Finite-element analysis of slopes and a field trial of a slope support system have shown that a considerable potential for excavation reduction exists if slopes are designed with variable slope angles with depth, and if artificial support systems are made an integral part of the slope design. A cost analysis has shown that the savings for a straight 500 ft. high slope with artificial support can amount up to $900 per foot of horizontal pit extension. Horizontal stresses and displacements can be overestimated by up to 100% by employing a two-dimensional finite-element analysis instead of a three-dimensional one. Stress magnitudes differ considerably when comparing results from slope models subjected to a gravity stress field with slope models subjected to high horizontal stresses. Because the latter case appears to be predominant for open pits, slope stability analyses have to be adjusted accordingly. A field trial measuring peak accelerations and displacements has shown that the use of pre- shearing for termination bench blasts, in cases of already heavily fractured ground, can be more detrimental than beneficial.

Jan 1, 1972

By Robert R. French

Beneficiation of low-grade nonmetalliferous mineral deposits by electronic color sorting is currently undergoing a period of rapid development. For those deposits in which the specific gravity, strength, soundness, and electric and magnetic properties of the ore and gangue are similar, the possibility of separation by color, reflectivity, or fluorescence offers hope for the utilization of much poorer quality ore than previously thought possible. For those ores in which consistency of color is required or for which a dry process is preferred, the electronic color sorter is particularly adaptable. Tests performed late in 1966 and reported herein are the result of continued interest in the dry beneficiation of gypsum and the development of higher capacity color-sorting machines. These tests should be considered only as an indication of the efficiency of the process and only with respect to the low-grade, untreated ore tested. Although most of the ore mined in Martin County, Ind., is of acceptable quality, a few thin carbonate strata and irregular nodules of dolomite and limestone are present within the main evaporite bed (Fig. 1).

Jan 1, 1969

By A. S. Malicsi, R. J. Lipp, I. Iwasaki

A loch-grade copper-nickel deposit, with an estimated 4.6 Gt (5 billion st) and average analyses of 0.6% copper, 0.2% nickel, occurs in northeastern Minnesota. In addition to copper, nickel, cobalt, and precious metals, the Duluth gabbro contains magnetite, ilmenite, olivine, plagioclase, and biotite. It u estimated that flotation tailings that would be produced by a concentrator of optimal size to sustain a smelter would amount to 20 Mt/a (22 million stpy). The flotation tailings, having already been ground, warrant a closer examination for recovery and use of potential byproducts. Residual sulfide minerals and fibrous minerals may also be isolated and treated separately for useful purposes or for disposal in an environmentally acceptable manner. Two flowsheets were developed; one involving preconcentration by low- and high-intensity magnetic separation and another involving preconcentration by gravity concentration. Concentration methods for recovering and purifying individual byproduct minerals were investigated. From their chemical, physical, and mineralogical characteristics, the potential areas of application and marketabilities of each product fraction were surveyed.

Jan 1, 1985

By Sidney A. Swensrud

This paper reviews the subject of gasoline margins, discusses some of the more current marketing problems, and gives some consideration to the main urges to marketing expansion, or overexpansion, in the oil industry. Margins In an earlier paper1, some comparisons were shown for the years 1929, 1930 and 1931, of the margin between the refinery cost of gasoline in Oklahoma, the market price in Oklahoma, and the average retail price in 50 representative cities of the United States. These figures indicated a small margin for the refiner in 1929 between his gasoline cost and the wholesale price, which, however, had turned into a loss by 1931. The margin between either refinery costs or wholesale prices and the retail price in the 50 cities showed a continuous decline during the three years. We have now worked out these figures on a similar basis for a longer period—from 1928 through 1936. The figures for refinery gasoline cost are slightly different from those in the earlier study, owing to the use of

Jan 1, 1937

AMONG the features that make Inspiration of outstanding A interest, particularly to the engineer, is the fact that at various times it has used, as a major method of production, three more or less distinct methods of mining and three distinct methods of treating its ores. The following chronology is of interest : Major Mining Methods: 1915-194 7 Underground block-caving, exclusively 1948-1952 Underground block-caving and opencut mining 1953-1954 Underground block-caving, opencut mining, and "glory-hole caved-block transfer" mining 1955 on Opencut mining and "glory-hole caved-block transfer" mining. Major Ore Treatment Methods: 1915-1925 Flotation concentration exclusively 1926-1930 Flotation concentration and ferric sulphate leaching 1931-1955 Ferric sulphate leaching (the so-called "Dual Process" was used for eleven months in 1937 when demand for copper was phenomenal; and the "leach-float" process was used for 24 months in 1942-44 as an expedient to help meet war demands for copper). 1956 on "Dual Process" combining a sulphuric acid leach followed by fine grinding and flotation of the residue from the leaching vats.

Jan 1, 1957

By Tom Learmont

The emergence of the dragline as the dominant stripping tool is described and reasons for this are noted. Brief comparisons are made with stripping shovels and wheel excavators. Representative output and machine availability figures for draglines are presented. The effect of changes in machine parameters such as boom length, swing power, and hoist power on machine productivity are discussed. An analysis of machine availability and the causes of machine downtime is made. Measures which are being taken to improve machine availability are discussed in detail. These include (1) improved methods of structural analysis, standardization of welded joints and welding methods to increase structural reliability and to develop more efficient structural designs, (2) standardization of gearing and mechanical componentry to permit the use of proven designs, (3) review of fairlead design and bucket hardware to improve rope life and reduce downtime, and (4) modifications to reduce maintenance time. The General Electric Data Logging system is described and consideration given to its use as a tool for improving productivity. Areas for future improvements in productivity are discussed.

Jan 1, 1976

By Charles J. Potter

There are many sources of energy available for consumption. Some available are solar, tide and wind. However, in terms of relatively large usage, only four principal sources are used for primary energy today. They are coal, oil, natural gas and water power. Such additional items as wood and nuclear energy, although supplying quantities of energy today, do not in the aggregate amount to any real significant quantity, but nuclear energy must be considered for future use. In addition, such a thing as gas from distillation of coal and oil is not considered primary energy. The principal markets for primary energy are the electric power utilities, space heating, industrial uses and transportation. The electric utility use of energy is primarily from coal, followed by natural gas and water power. Space heating is primarily a gas market, followed by oil and then coal. Space heating by electricity is only considered in the generation of electric power. Transportation's principal source of energy is oil. Coal has practically no market left in this field.

Jan 4, 1962

By W. J. Houk, F. C. Hull

To clarify interpretations of grain structures and to assist in calculations of spatial grain size distributions, plane distribution curves have been determined for random sections through four regular polyhedrons approximating the shapes of metal grains. The characteristics of the distribution curve for the average metal grain are predicted. IT was realized early in the history of metallurgy that metals are polycrystalline aggregates and that the size and shape of crystals affects the properties of the material. Reaumur1 in 1722 employed the microscope to examine the fractured surfaces of steel and of white and gray cast iron and suggested a polyhedral arrangement of the crystals. The first extensive investigation of the form of crystal grains was carried out by Desch.2 He examined the disintegrated grains from a ß brass sample and noted that the number of faces per grain ranged from eleven to twenty and that the number of edges per face varied from three to eight and the maximum occurred at five. While it has been found practical to examine isolated grains only in exceptional cases, it is always possible to make a plane section through the metal and examine the shape of the grain sections on the plane of polish. Desch2 tried to determine the relation between the form of a polyhedron and that of its plane sections for comparison with distribution curves of numbers of sides per grain section of actual metal samples. The polyhedrons investigated were the rhombic and pentagonal dodecahedrons and the orthic tetrakaidecahedron. However, the frequency distributions of the number of sides of plane intersections were not sufficiently characteristic to decide which polyhedron most closely approximated the average grain in a metal. Determination of Statistical Shape of Grain in Space Scheil3 was interested in the problem of calculating the distribution of grain sizes in space from the easily measured distribution of grain section sizes on the plane of polish. Assuming that the grains were spheres and using the plane distribution curve for a sphere shown in Fig. 1, he employed a successive subtraction method to calculate the spatial distribution. In order to evaluate the accuracy of these calculations, Scheil and Wurst4 determined the actual distribution of grain sizes in space in their sample of ingot iron by polishing off successive layers and following every individual grain in a series of micrographs. From curves of mean radius of intersection of a given grain vs thickness of metal removed in polishing, Scheil and Wurst attempted to derive the statistical shape of a grain in space. Their calculated plane distribution curve for this shape is compared with the distribution curve for a sphere in Fig. 1. A table of values based on this curve was prepared for calculating spatial distributions of grains. The calculated and measured spatial distributions of their sample then agreed much better than when a spherical shape had been assumed. In the present paper, an attempt has been made to learn something about the average metal grain by studying in detail the effect of the shape of regular polyhedrons on the plane distribution of areas and shapes of areas produced by random sections through them. From the data presented below, it can be concluded that the plane distribution curve for the average metal grain differs in three fundamental respects from the curve derived by Scheil and Wurst. Polyhedrons Selected for Study The polyhedrons selected for the statistical study are illustrated in Fig. 2 and consisted of a cube, a figure formed by cutting off the corners of a cube at the midpoints of the original edges, a tetrakaidecahedron, and a pentagonal dodecahedron. The length of edge on any one figure is a constant. For the above models the edge lengths were 3.50, 4.00, 2.00, and 2.08 in., respectively. A cube was selected for one of the polyhedrons because of its simple geometry, because it is a form that by repetition can completely fill space, and because it represents a convenient degree of departure from compactness beyond which the shape of

Jan 1, 1954

By J. W. Sandelin, L. S. Birks

The group five metals, vanadium, niobium, and tantalum all show cold-rolled textures of {100)(011) and {112)(0ll) with a preference for the (100) in vanadium and niobium and for the {112) in tantalum. Recrys-tallization texture of (100) and (111) was reported1 for vanadium after annealing (no temperature stated). For tantal~m ,~ annealing below 1200°C strengthened the (112) texture but the (111) texture increased and was predominant as the annealing temperature was raised to 2500°C. Annealing niobium up to 1100°C strengthened the ( 100) texture and developed a weak (111) texture.' In the present work niobium has been annealed up to 2000°C. Nearly 70 pct of the grains showed {111) texture with only a weak (112) component and an insignificant (100) component remaining. In addition, double-crystal rocking curves were used to follow the increase in crystal perfection of the grains with increased annealing time. Material and Treatment. Samples i by 4 in. were sawed from & -in.-thick cold-rolled niobium sheet obtained from Wah Chang. Chemical analysis of the material showed it to be 99.4 pct pure with tantalum as the major impurity. Individual pieces were annealed for 2, 15, 30, and 60 rnin in a vacuum of 10'* Torr using an rf generator. They were etched until the grain boundaries were well-defined, Fig. 1. Average grain size varied from 1 mm for 2 min annealing to 2 mm for 60 rnin annealing. Experimental Results. Preferred Orientation. The orientations of 97 of the 117 grains in the specimens of Fig. 1 were determined by back-reflect ion Laue patterns. A General Electric 10-cm-diam cylindrical camera was used rather than the conventional flat camera in order to record more of the low-index spots. The method proposed by Forest, Barton, and schieltz4 was used to transform the cylindrical film patterns to standard stereographic projections. Table I gives the compilation of data. Even 2 rnin anneal at 2000°C is sufficient to yield a strong (111) preferred orientation, and the percentage of grains with this orientation increases steadily with annealing time at the expense of all other orientations. Crystal Perfection. X-ray topographs were taken of each specimen in both the (111) and (112) orientation using the method described by Birks and Grant.' As the anneal time increases, the grains become larger and the individual reflections become slightly more uniform in intensity, indicating an increase in crystal perfection. For a more quantitative measure of crystal perfection, it was necessary to measure the double-crystal rocking curve. The spectrometer employed was a Gaertner instrument of Compton design. LiF was chosen for the first crystal because the (400) reflection with d spacing of 1.05 AU is a good match to the (222) niobium reflection with d spacing of 0.95 AU. CuKp radiation was used in order to further reduce the d spacing mixmatch correction.' A variable aperture was placed between the LiF and the niobium specimen so that a single grain or even a small portion of a grain could be examined. Fig. 2 shows typical rocking curves for the four annealing times. For the 2-min specimen, a single peak is observed with 10' of arc full-breadth at half maximum. As the annealing time is increased to 15 or 30 min, several sharper peaks of 40 to 80" breadth can be seen within a single grain. After 60 rnin anneal only a single peak of about 30" is observed. Table I1 shows the corrected rocking curve breadths and the dislocation densities, ND. The latter were calculated from the equation7 where W is the corrected rocking curve breadth at half maximum in radians and b is the effective Burger's vector. For (110)(111) slip in niobium, b is 2.86 AU. Discussion. The annealing of cold-rolled niobium at 2000°C causes rapid preferential growth of grains with {ill} orientation. After only 2 rnin annealing time, 35 pct of the grains have the (111) orientation, and after

Jan 1, 1968

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.' The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.' There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.' The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By J. K. Elliott, P. H. Kelly

Many engineering functions such as surface metering work and laboratory compressibility check points involve the use of liquid densities of light hydrocarbon mixtures at various pressures and temperatures. However, at the present time, no simple reliable method exists for determining density variation, particularly if the composition of the liquid is unknown. Consequently, a study was undertaken to develop and present a simple and accurate method of predicting density variation of a light hydrocarbon liquid with pressure and temperature, knowing only the density of the liquid at some condition. The experimental liquid compressibility data from API Project 37 by Sage and Lacey' have been considered to be accurate within 0.5 per cent and cover a wide range of pressure (14.7 to 10,000 psia), temperature (100" to 400°F) and molecular weight (up to 150). From these data, a set of liquid density curves, which relate density to pressure, temperature and molecular weight, was developed. These curves make it possible to predict density variation with pressure and temperature. Compared to extensive laboratory compressibility data on a complex, light hydrocarbon liquid, the use of the liquid density curves resulted in an average error of less than 0.5 per cent. Based on the results of this analysis, it is concluded that the set of liquid density curves developed from the data of Sage and Lacey provides an accurate and simple method for predicting the density variation of light hydrocarbon liquids when the density at some condition is known. These curves should be very helpful in many engineering calculations, particularly in the surface metering of light hydrocarbon liquids. INTRODUCTION Many situations arise in field and engineering laboratory work, such as reservoir engineering studies, check of experimentally determined laboratory data and orifice flow-meter formulas, where liquid density factors at various pressure-temperature conditions are required. Also, the need for accurate light hydrocarbon liquid information has become more important with the advent of miscible-type displacements for secondary recovery purposes in oilfield operations. Several reliable methods are available1 - "or determining the density of liquid hydrocarbons if the composition of the liquid is known. However, there is a definite lack of methods for accurately determining the variation of density when the composition of the liquid is unknown. The purpose of this study is to review the various methods for determining hydrocarbon liquid densities and to develop a simple and reliable method of determining variation in density of light hydrocarbon liquids with pressure and temperature when the compositio~n of the liquid is unknown. METHODS FOR DETERMINING DENSITY OF LIQUIDS OF KNOWN COMPOSITION Sage, Lacey and Hicks' have proposed a method to predict the density of light liquid hydrocarbons by using partial molal volumes. Data are available on experimentally developed partial liquid volumes of hydrocarbons over a rather limited range of temperature, pressure and composition. The partial mold volume method has proved satisfactory for determining the density of some hydrocarbon liquids when the composition is known. Within the range covered in the Sage, Lacey and Hicks1 data, the results agree within about 3 per cent of the experimental values. Hanson mentions the limitation of this method to a composition range of approximately 10 per cent by weight of methane, which will not allow this correction to cover most low molecular weight-light hydrocarbon liquids. Standing and Katz2 studied data on light hydrocarbon-liquid systems containing methane and ethane at high temperature and pressure and have presented a method for determining liquid densities, assuming additive volumes for all components less volatile than ethane and using apparent densities for methane and ethane. The compressibility and thermal-expansion curves used by Standing are based on assumptions that compressibility of a hydrocarbon liquid at temperatures below 300°F is a function of the liquid density at 60°F and that thermal expansion of the liquid is affected little by pressure. The information required to use this technique with an example problem is furnished by Standing.' Hanson eports an average error of - 0.5 per cent using the method of apparent densities in calculating liquid densities of several volatile hydrocarbon mixtures. However, as implied, the apparent density method is not applicable for liquid density calculations when the composition of the liquid is unknown. Watson- as presented a method

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965