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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 John M. Dale

Sulfur has attractive features as a base material for coating systems. It melts at 246ºF and can be applied as a liquid above this temperature. Its melting point is just above the environmental stress level, 180°F, for most coatings and yet it is low enough to be easy to work with in comparison to many hot melt systems. The viscosity characteristics are such that sulfur lends itself to spray applications. The oxidation rate of sulfur in the atmosphere is very low and sulfur has outstanding chemical resistance characteristics, particularly in acid environments. One of the greatest potentials for these coatings appears to be in the protection of other materials. At one time, most acid tanks and pits were constructed with acid- proof brick and sulfur based mortars. This type of construction is much more expensive than sulfur based spray coatings. An attractive sulfur based coating composed of sulfur, talc, milled glass fibers and dicyclopentadiene,1 developed by the Institute for the Bureau of Mines has excellent acid assistance and can be used to protect concrete from acid attack.

Jan 10, 1973

By R. W. Armstrong, P. C. Jindal

TABOR1 has indicated for a number of polycrystal-line materials that their hardness should be directly related to their yield strength. For a material showing zero work-hardening, the Meyer hardness, MH, may be calculated in terms of the yield stress, sy, by utilizing slip line theory and the result is: The Meyer hardness corresponds to indenting the surface with a spherical indenter and specifying the ratio of load and projected area of the indentation. The correlation indicated by Eq. [I] is not well-established. It has been verified to some degree by performing hardness tests on materials strained to the maximum nominal stress and taking this stress as the (new) yield stress of a nonwork-hardening material. The dependence of hardness on yield strength for an annealed material capable of showing work-hardening has not been theoretically evaluated but, presumably, the hardness should be greater than that specified above. Marcinkowski, Fisher, and szirmae2 measured the dependence of the Vickers Diamond Pyramid hardness, H,, on yield strength for an annealed Fe-Cr alloy which shows work-hardening and found:

Jan 1, 1968

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 H. H. Waller, C. H. Brehaut

At the Jeffrey mine of Canadian Johns-Manville Co. in Asbestos, Que., automatic batched concrete from surface is placed underground pneumatically for distances of 2500 ft directly into forms or to a second placer for greater distances, through 6-in. pipe of high carbon steel. The use of Celite C-4-C in addition to the usual aggregates achieves greater compressive strengths, lowers cost, reduces segregation, and improves workability and placeability results. Each year 25,000 cu yd of concrete are placed without interrupting production and development work in the mine, making possible a cheaper concrete that can be poured wherever and whenever it is needed. In about 90 pct of the underground openings in the Jeffrey mine concrete is necessary to preserve them in their original sizes and shapes for production. In the remaining 5 pct, the greater portion is united with or without steel support. When large quantities of concrete were forecast for underground use at the Jeffrey mine, preliminary and first hand information regarding pneumatic placing was acquired from articles by Bernhardt and Swanson and visits to their respective mines.

Apr 1, 1956

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 N. J. Myers, S. J. Nemeth

POWER in the mill at Appalachian Sulphides Inc. is provided by 86 electrical motors ranging from 1 to 200 hp and totaling 1200 hp. After a careful study of different types of support for these cables an expanded metal trough was chosen as the most suitable. One hundred and twenty feet of trough were installed in 18-in. width and 150 ft in 6-in. width. This trough carries all the power as well as the control circuits. Now that the electrical distribution system is complete it is clear that this type of cable supporting system offers many advantages. To handle the same amount of cable in conduit, for example, would have required such a jungle that wiring all the different motors and controls would have been very difficult, even for the original hook-up. In the Appalachian Sulphides operation it has been necessary to make changes from time to time in the wiring of the different motors. These changes are readily made with the present cable supporting system because the trough leaves the wires accessible for rerouting as needed.

Jan 1, 1958

By A. W. Griffith, R. G. Beverly, W. A. Millsap

THE Grand Junction Pilot Plant, operated by National Lead Co. Inc., for the U. S. Atomic Energy Commission, is engaged in the amenability testing of orebodies to establish design and cost data for commercial mills and to test new processes for recovery of uranium from ores. Test work was performed to study the effects of several variables on leaching of uranium ores in carbonate solutions. Many of these variables had been investigated in the laboratory, but pilot plant tests were desirable to evaluate their importance in semi-works equipment and to predict optimum operating conditions for future commercial mills. The results of these tests should serve as a guide in selecting the most efficient and economical method of leaching uranium ores amenable to a carbonate process. This article is concerned with a process in which uranium is extracted from the ore by a hot Na2CO3- NaHCO3 solution; the uranium-bearing solution is separated from the solid residue by filtration, and uranium is then precipitated by chemical means.

Jan 9, 1957

By H. A. Guess

Introduction. History and Production Statements. Southeast Missouri is the oldest of the large producing districts of the United States. The first recorded production from disseminated ores was in 1869, although for many years prior to that time lead had been milled from shallow pockets, and steady growth in production has been shown ever since, the greatest increases being during the past five years. The production by years for each of the operating companies from 1869 to 1907, inclusive, is given in Table I. In Table 11. is given the production by years from 1908 to 1912, inclusive, for the district as a whole, showing the tonnage of crude ore mined, yield in concentrates, average assay of concentrates; yield in metallic lead both per ton of crude ore and in total; also approximate value of the yearly production. It is interesting to note that the production for the 5-yr. period 1908 to 1912, inclusive, is practically equal to the total previous production, viz., the 39-yr. period 1869 to 1907, the summary being as follows:

Jan 1, 1915

By G. R. M. Del Giudice

A survey of the flotation literature of the past 10 years indicates an increasing use of the microscope as a tool for investigation. Thus, the metallurgical microscope has been used by Tucker and Head;' Taggart, Taylor and Ince;2 Ince,3 and del Giudice4 to examine mineral surfaces that had been subjected to the action of various flotation reagents and to the action of slime pulps. It has also been used by Gaudin, Groh and Henderson;5 Martin;6 Morrow and Griswold;7 and others to examine bakelite briquets of mill products. The microscope with transmitted light, both with bright-field and dark-field illuminations, has been used by Taggart, Taylor and Knoll8 and by Ince9 to observe Brownian motrement and flocculation in flotation pulps. The use of the microscope at low-power magnifications with incident illumination for the examination of mill products has been known for years.10 Finally, del Giudice11 has used a relatively new type of illumination, the Ultropak, for the examinntion of slime-coatings.

Jan 1, 1935

By E. Horton Jones

INTRODUCTION WE have endeavored in the following "sheets" to give the unit construction costs derived from the building of the Arizona Copper Co.'s new smelter, Clifton, Ariz., starting in February, 1912, and completing February, 1914. 1 In Chapter I-Unit Costs-are to be found the most elementary total unit costs which the accounts provide for. They are usable in the Clifton district. Here too are found the percentages to be added to an estimate for Engineering and General Expense. In Chapter II-Comparative Costs-these elementary costs have been classified, averaged and reported as labor and material unit costs. In such form the labor unit costs, when properly applied to similar conditions as these under which they were derived, are usable anywhere. The material unit costs are better disregarded for more accurate estimates and replaced by a newly priced bill of material. In Chapter III Composite Costs are given. They are unit costs built-up from several elementary units, and likewise units of larger dimensions and simpler application, valuable for

Jan 7, 1914

By D. G. Oss, S. E. Erickson

An automatic control method for the ferrosilicon heavy media process maintains media density within 0.01 specific gravity points. Continued demands for higher grade, competitive products from the Mesabi Range have resulted in experimental work such as that detailed for one concentrator. Various methods, step by step procedures and instruments used at an iron ore beneficiation plant in the development of an automatic control system are described. Work continues and it is hoped that further applications of control instrumentation can be made in the next operating season. The need for instrumentation and automatic control of the various parameters in the heavy media process of iron ore beneficiation has been apparent for some time. Continued demands for higher grade, competitive products from the Mesabi Range have made it necessary to increase the efficiency of the process in every possible way. In a typical heavy media flow scheme for iron ore beneficiation (Fig. 1) a sized, prepared feed (generally about —1% in. to +% in.) is fed to a heavy media separatory vessel, along with a ferrosilicon slurry. A separation of the feed is made on the basis of specific gravity. Low density particles overflow a tailings discharge weir, while high density ore particles sink to the bottom of the high density pool and are moved away to the concentrate discharge chute. Both products are passed over drainage screens and then are cleaned thoroughly of attached ferrosilicon on wash screens. Float material is generally stockpiled, while the sink product is shipped as a final concentrate. Undersize from the drain screens is returned directly to the circulating media sump. Wash screen undersize is cleaned of contaminating ore particles and slimes by passing through magnetic separators. Provision is also made for splitting a portion of the tailings drain undersize into the cleaning circuit if necessary for control of depth of tailings overflow, or for additional cleaning as required. Cleaned ferrosilicon is stored in a densifier and returned to the Circulating media sump as make-up material. Dilution water is also added to this sump to maintain a desired specific gravity of the circulating media. As in any process, operational intelligence is secured only by keeping records of the process variables. Generally apeaking, plant operators have neither the inclination nor the time to keep complete and detailed records of these variables over the course of their shift. Before instrumentation was added to aid the operator, specific gravity was measured by weighing a given volume of pulp at intervals of from 30 to 60 min. Scale readings were made at the beginning and end of each shift. No records were kept of operating conditions, such as rpm of the separatory ves-sel, media level in the machine, tons per hour of the products, and so forth. These items were recorded only when spot checks were made by the metallurgical staff. CONTlNlJOUS DENSITY RECORDING The first process instrument used, other than the usual ammeter on the drive motor of the separatory vessel, was a nuclear density gauge and its associated circular chart recorder. These instruments were used to indicate and record specific gravity of the circulating media. This was a tremendous aid to the operator in that tie was able to observe and correct the specific gravity at any time. There was also added incentive to make frequent corrections because of the permanent record made by the recorder of the densities. The addition of the nuclear density gauge was influential in securing optimum quality and recovery of the heavy media product. Manual control was improved, and it became possible for a good operator to main control within f.05 specific gravity units. This compares with an unknown quantity, estimated at f0.15 gravity units, when manual measurement and control was used. An example of the improvement in manual control over the course of one season's operations is shown in Fig. 2. Chart A is typical of the records made shortly after the gauge was installed. Needless to say, it was difficult for operators and foremen alike

Jan 1, 1962

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 K. N. Weaver

In the early 1950's the cement industry began putting a new emphasis on geology. This article points up some of the industry's raw materials problems that geologists are uniquely qualified to handle. Portland cement can be made from relatively abundant industrial minerals and rocks, and this may explain why cement producers placed little emphasis on geology during the early days of the industry. After World War 11, however, the industry began to recognize the need for geological exploration and some of the larger companies began to build a permanent geological staff. This development has its roots in: 1) The rapid expansion of the industry. After World War II and continuing into the early 1950's the demand for cement far exceeded the production capacity. This placed a great deal of pressure on the producers to enlarge capacity at their plants and to develop new sites. 2) The closing of many cement plants due to inadequate raw materials. Producers feared lack of raw materials due to inadequate exploration and evaluation. 3) An ever increasing pressure for upgrading of the quality of portland cement, necessitated upgrading the quality of raw materials. 4) The increasingly large capital investment needed to build new cement plants required a higher degree of accuracy in reserve calculation. These reasons are more or less self explanatory and will not be elaborated on. They are outlined to illustrate the probable evolution of thought among cement management to justify the development of a geological staff. In the author's personal experience the geologist must continually readjust to changing conditions within the industry. For example, cement production capacity grew so rapidly that today production is only about 70% to 75% of rated capacity (73.8% in 1963). Therefore, whereas the geologist's function during the active expansion of capacity was primarily one of exploration, one of his major functions today is the development of existing reserves. This assumes of course that reserves at existing plants have been proven to be adequate in terms of the company's reserve policy. Through the proper development of raw materials, the geologist can markedly influence quality control, production and long range planning. Examples of several of the operations of Medusa Portland Cement Co. will illustrate how proper attention to geologic detail pays off in the above areas. Because limestone is the major raw material of port-land cement, the examples will be concerned with it. DEVELOPMENT OF GEOLOGIC DETAIL One of the prime objectives of an exploration or development project should be the establishment of the stratigraphy and structure of the deposit. The basic tool for exploration and development is still the core drill, and the geologist must gain a maximum amount of information from a minimum amount of drilling. In order to obtain this objective the following is essential: 1) Adequate detailed geologic logging of cores. The core is first logged and separated into lithologically distinct units. In order to make the lithologic breaks as meaningful as possible, representative pieces of core (not all) are etched in dilute HCI. This removes the "drill polish", brings out the structure of the rock and indicates the proportion of dolomite and argillaceous material because dolomite and argillaceous material etch in relief. In this way the lithologic breaks become clearer and one gains a general idea of the chemical makeup before analysis. This method of logging lessens the probability of including two types of stone, e.g. limestone and dolomite into the same sample for chemical analysis. 2) Representative sampling for chemical analysis. After logging, the lithologic units are sampled for chemical analysis. A representative analysis can be obtained by extracting a 1-in. sample for every foot of core. For example, a lithologic interval of 10 ft to 20 ft would yield ten 1-in. samples taken at 11 ft, 12 ft, 13 ft... and 20 ft. These samples are then crushed, pulverized and split into a sample for chemical analysis. This sampling method represents a significant saving of time over splitting the entire core. 3) Preparing the core as a record. Because of the expense of storage and the difficulty of handling large amounts of core, only representative samples of each lithologic unit are saved for reference. An

Jan 1, 1965

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

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 W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951