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By T. M. Geffen, F. F. Craig

Laboratory model flow tests have been made to simulate field conditions of partial pressure rnaintenance by dispersed gas drive on rocks having sandstone-type porosity. In this production method there is a significant saturation gradient between injection and production wells. A means of calculating relative permeability characteristics. from partial pressure rnaintenance flow tests has been developed. This method takes into account the saturation gradient. These kg/ko characteristics are identical to those for solution and external gas drives. This method of calculation, which has been proved experimentally, has limitations; however, it is valid for cases likely to be encountered in field prediction of partial pressure maintenance performance. The production performance of a hypothetical reservoir has been calculated for several different injection programs, involving both full and partial pressure maintenance. Results indicate that the maxinum oil recovery by these gas injection programs is obtained by full pressure mainte- nance at the original bubble point. Correspondingly lower oil recoveries are obtained by postponing gas injection and/or by reducing the degree of pressure maintenance. INTRODUCTION Dispersed gas injection is an important method of recovering additional oil beyond that obtainable by pressure depletion alone. The injected gas acts as a source of additional energy to displace oil from the rock formation as well as to retard oil shrinkage in the reservoir. In practice, gas injection is usually started after the reservoir pressure has fallen below the original bubble point. For various reasons sufficient gas is generally not injected to completely maintain the pressure in the reservoir. So, injecting gas at a declining reservoir pressure results in a combined external and solution gas drive. These two oil displacement processes are characterized by different gross saturation distributions in the reservoir. The external gas drive, like all frontal drive processes, inherently results in an oil saturation which increases from the injection wells to the producing wells. In the solution gas drive there is essentially a uniform oil saturation throughout the reservoir, provided the field is being depleted uniformly. It has been customary to predict oil recovery performance under partial pressure maintenance by a method which does not take into account the saturation gradient1. It has been shown2 that neglecting the presence of a saturation gradient can cause considerable error. It is the purpose of this paper to develop and present an improved method of predicting partial pressure maintenance performance of reservoirs including, where necessary. the effects of well arrangement. From the laboratory standpoint, this problem involves the measurement of the basic flow behavior (relative permeability characteristics) under partial pressure maintenance conditions. Recent research- as shown that for rocks having sandstone-type porosity, the relative permeability characteristics are identical for solution gas drive and complete pressure maintenance external gas drives. Since both solution and external drives have the same basic flow behavior, it was speculated that partial pressure maintenance, being a combination of the two, would also

Jan 1, 1957

By J. J. Bikerman

In a recent study' of the martensitic transformation of Cu-Zn ß-phase alloys, it was noted that the MS temperature at the surface was raised due to the loss of zinc by volatilization. It seems likely, therefore, that the MS temperature may serve as a guide for the measurement of composition. From a knowledge of the dependence of the transformation temperature on composition, 2 it should be possible to detect variations in zinc content which are less than 0.1 at. pct by measuring the MS temperature throughout the sample. It is unlikely that an electron microprobe analysis could detect accurately such small zinc losses because the presently accepted limits of accuracy of the micro-probe analysis in simple ternary systems are of the order of 2 to 5 pct of the amount present.3 In the present study, a composition gradient was produced by precipitating the a primary solid solution, and reheating for a very short time within the 0-phase field. The nominal composition, in atomic percent, of the ternary ß-phase alloy used, 64.2 Cu, 34 Zn, 1.8 Si, was selected because it had an MS temperature of +4°C, thereby simplifying the experi-

Jan 1, 1968

By William Paxton Hewitt

The San Carlos lead deposit in northeast Chihuahua yielded approximately one million tons of galena ore from a blanket-like deposit. Countryrock, composed of Cretaceous limestones and calcareous shales as old as late Albian-early Aptian, and an underlying undated quartzite series, has been warped into a northwest trending anticline and has been invaded by a light-colored holocrystalline igneous rock. Magnetite and contact metamorphic minerals heterogeneously mixed with variable amounts of pyrite, sphalerite and galena, are concentrated along the anticlinal axis where they replaced magnesia-rich argillaceous sediments above the quartzite contact. Magnetite and associated silicates were deposited under near-contact conditions. Following a period of post-magnetite shattering, pyrite, sphalerite and galena were introduced at lower temperatures. Galena and associated dolomite or magnesite, the final phase of mineralization, are concentrated at the top of the deposit near the anticlinal crest and extend upward into isoclinally folded dolomitic argillites. INTRODUCTION AND ACKNOWLEDGEMENTS The stoped outlines of the San Carlos Mine are a pattern for a stratiform blanket-like deposit. But the close association of mineralization with an anticlinal axis, an observed relation between high grade galena mineralization and the apices of isoclinal folds, and the petrographic story of mineralization introduced into shattered areas make the deposit an example of structural control of ore de-

Jan 1, 1970

By Fred C. Bond

DISCUSSION Milton C. Shaw and Donald R. Walker (Massachusetts Institute of Technology)—For many years the two empirical rules of comminution bearing the names of Rittinger and Kick have been applied to grinding processes to account for the energy required to crush brittle materials. The basis for Rittinger's rule was the thought that the energy to grind a substance went largely into supplying the additional energy associated with the new free surface, while Kick's law was prompted by the concept of dimensional similarity and is a special statement of the concept of constancy of strain energy to cause rupture. According to Rittinger the energy to grind a given volume varies as the change in the square of the mean particle size, v - A (D2), while according to Kick this energy varies

Jan 1, 1953

By Fred C. Bond

DISCUSSION Milton C. Shaw and Donald R. Walker (Massachusetts Institute of Technology)—For many years the two empirical rules of comminution bearing the names of Rittinger and Kick have been applied to grinding processes to account for the energy required to crush brittle materials. The basis for Rittinger's rule was the thought that the energy to grind a substance went largely into supplying the additional energy associated with the new free surface, while Kick's law was prompted by the concept of dimensional similarity and is a special statement of the concept of constancy of strain energy to cause rupture. According to Rittinger the energy to grind a given volume varies as the change in the square of the mean particle size, v - A (D2), while according to Kick this energy varies

Jan 1, 1953

By L. O. Bacon, D. O. Wyble

THERE has been considerable speculation among mining geologists and mining men in general as to the relative merits of gravity methods in iron-ore exploration. Most of the investigations which have been carried out in recent years have been done by mining companies, and few if any of the results have been published. Three gravity surveys have been made in the Iron River-Crystal Falls area,1,2 one by the U. S. Bureau of Mines, with inconclusive results, and the other two by Radar Exploration Co. for the Cleveland-Cliffs and the M. A. Hanna companies, with results not known to the writers. Both the last-mentioned surveys were detailed investigations, the stations being spaced as close as 10 ft along traverses,1 and were made to determine the feasibility of locating iron ore by gravitational methods. Because of the presence of a large body of ore already extensively drilled, Dr. Harold L. James of the U. S. Geological Survey, Iron River, Mich., suggested that a further test of gravitational methods of exploration be made in the Round Lake area of Iron County, see Figs. 1 and 2. This survey indicated a considerable regional gradient and led to a study of the surrounding gravity field and its relation to the major structural features of the syncline within which the iron formation lies. The southwestern part of Iron County presents a series of hills and hollows elongated in a roughly north-south direction. The bedrock topography is of pre-glacial origin. Relief is moderate; a maximum elevation difference of approximately 350 ft was observed during the survey. Major drainage is dendritic with the larger streams: the Brule to the south, the Paint to the north, and the Iron in the central part. Hills are thickly grown with hardwoods, and lowland areas, not under cultivation, are usually covered by second-growth softwoods. The area covered in this paper includes the southern half of Iron County, Mich., with a deep synclinal basin occupying the central part of the area, and the southeast corner of Gogebic County, immediately to the west of Iron County. The upper Huronian iron formation, slates, and graywackes which form the synclinal basin rest upon a greenstone basement. The basin has not been completely outlined by exposures, drill records or other means, as outcrops are scarce and the thick mantle of glacial drift makes geological investigations extremely difficult. Glacial drift varies in depth up to 300 ft or more. The drift is usually thickest under the hills and is thinnest in the depressions and along drainage courses where most of the bedrock exposures occur. The area over which gravity investigations were made is almost entirely covered by glacial material. Bedrock of the basin consists of a complexly folded series of iron formation, slates, and graywackes. One of the series of slates has a high magnetic susceptibility due to the fine-grained magnetite it contains. This formation can be detected readily by magnetic methods and provides a marker horizon which can be easily followed. The magnetic slates are stratigraphically above the iron formation, and much of the geological interpretation of the area is based upon the magneticc anomalies they produce.

Jan 1, 1952

By B. E. Eakin, A. L. Lee

Atmospheric pressure viscosity values For light hydrocarbons were calculated by a simple mixing rule based on the Sutherland constants for pure components. This method was further extended so that the atmospheric pressure viscosity of a mixture may be calculated based on the molecular weight information only. INTRODUCTION A proven method for estimating the gas-phase viscosity of a mixture is the one by Herning and zipperer.l This mixing rule has the following form: One method for calculating the pure component viscosity i is the Sutherland equation,2 which has the following form: The Sutherland constants B and S are determined from experimental data. A set of Sutherland constants for light hydrocarbons based on the data of several investigators3-5 is presented in Table 1. APPLICATION The Herning-Zipperer equation and the Sutherland equation were used to obtain an equation for calculating the gas-phase viscosity of light hydrocarbons. This equation has the form, Eq. 3 was used successfully in the study of methane-n-butane mixtures.6 Further analysis indicated that the Sutherland constants are a function of molecular weight.7 The gas-phase viscosity may be calculated based on molecular weight information only. The following equation was developed: The atmospheric pressure viscosity of ethane, propane, n-butaneand four methane-propane mixtures calculated on the basis of Eq. 6 are compared with the data of other investigators in Tables 2, 3, 4 and 5, respectively. A plot of atmospheric pressure viscosity vs molecular weight based on Eq. 6 is presented in Fig. 1.

Jan 1, 1965

By Behram H. Wadia, Robert S. Lehto

A new metallurgical treatment for capturing as much of the values as possible from zinc refinery feed has been devised by personnel in Cerro de Pasco's Peruvian operation at La Oroya. Results from a pilot test illustrate that 50 metric tons of throughput can be maintained whereby substantially all the silver and copper report in the sponge iron while zinc and lead with indium and cadmium volatilize in the fume. This new technique named the Zileret (zinc leach residue treatment) process complements the electrolytic system used in the refinery so that all values in a zinc concentrate are economically recovered. In the system, dried zinc leach residue is pelletized with soluble zinc sulfate which already exists in the leach residue and a finely divided reducing agent such as anthracite coal. Upon heat addition, the loose anthracite in the charge maintains a reducing atmosphere while the free space above the charge has an oxidizing nature. When the charge reaches the reaction zone at about 1100°C, metals such as zinc, lead, cadmium and indium volatilize from the pellets, are oxidized in the upper kiln atmosphere, and are then carried in suspension as an oxide fume to the cooler and baghouse. The copper and silver content in their reduced forms, along with the iron, discharge from the kiln as a calcined product which is then cooled to below 130°C before being exposed to the air.

Jan 9, 1969

By R. B. Gilmore, Lewis W. MacNauhgton

The North Texas district, as' herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wilbarger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, usually are modified by stratigraphic changes in the sediments. Excepting those in southeastern Baylor, southern Archer, and southwestern Clay counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsyl-vanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1942 Approximately 500 wells were drilled in the district during 1942, in contrast with some 1600 wells drilled during 1941, and only some goo oil wells were completed, a decrease from 1941 of more than 10 per cent in the number of successful drilling operations of the total wells drilled. Production increased slightly over the previous year in spite of a decrease in the number of producing wells. The average depth of discovery wells was some 600 ft. deeper than in 1941. Although more discoveries produced from horizons above the base of the Strawn series than those below the Strawn, the deeper horizons, including the Bend series of the Pennsylvanian, the Mississippian limestone, and the Simpson and Ellenburger of the Ordovician, furnished most of the addition to oil reserves. The largest single addition to the reserves was again in the Ellenburger formation in the K. M. A. field. During the year 47 wells were completed, bringing the total developed acreage in this horizon to some 5450 acres. The most active area was Montague County, in which eight fields, or potential fields, were discovered although only 39 oil wells were completed. K. M. A: Pressure Maintenance Satisfactory progress was made by the K. M. A. Pressure Maintenance Association in 1942, At the end of the year, 100 wells were being used for input and total monthly volume of gas returned to the reservoir reached a high of 430,971 M cu. ft. in December, with an input ratio of 587 cu. ft. of gas returned for each barrel of oil produced during the month. This represents a utilization of 50 per cent of the gas available for return during that month. Comparison of the present average bottom-hole pressure by means of a decline

Jan 1, 1943

By R. B. Gilmore, Lewis W. MacNauhgton

The North Texas district, as' herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wilbarger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, usually are modified by stratigraphic changes in the sediments. Excepting those in southeastern Baylor, southern Archer, and southwestern Clay counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsyl-vanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1942 Approximately 500 wells were drilled in the district during 1942, in contrast with some 1600 wells drilled during 1941, and only some goo oil wells were completed, a decrease from 1941 of more than 10 per cent in the number of successful drilling operations of the total wells drilled. Production increased slightly over the previous year in spite of a decrease in the number of producing wells. The average depth of discovery wells was some 600 ft. deeper than in 1941. Although more discoveries produced from horizons above the base of the Strawn series than those below the Strawn, the deeper horizons, including the Bend series of the Pennsylvanian, the Mississippian limestone, and the Simpson and Ellenburger of the Ordovician, furnished most of the addition to oil reserves. The largest single addition to the reserves was again in the Ellenburger formation in the K. M. A. field. During the year 47 wells were completed, bringing the total developed acreage in this horizon to some 5450 acres. The most active area was Montague County, in which eight fields, or potential fields, were discovered although only 39 oil wells were completed. K. M. A: Pressure Maintenance Satisfactory progress was made by the K. M. A. Pressure Maintenance Association in 1942, At the end of the year, 100 wells were being used for input and total monthly volume of gas returned to the reservoir reached a high of 430,971 M cu. ft. in December, with an input ratio of 587 cu. ft. of gas returned for each barrel of oil produced during the month. This represents a utilization of 50 per cent of the gas available for return during that month. Comparison of the present average bottom-hole pressure by means of a decline

Jan 1, 1943

By G. L. Hassler, E. Bruner

An apparatus and method is described whereby the relation between saturation and capillary pressure under decreasing saturation can be quickly determined for small core samples. The initially saturated core is cen-trifuged at increasing rates and the average saturation is measured at each rate with the aid of a stroboscope device. A theory and calculation procedure is given whereby the accelerations and saturation values can be converted into a true curve of capillary pressure versus saturation. The present work differs from previously described use of the centrifuge to obtain capillary-pressure curves of core samples3 in that the core is centrifuged alone, so that the whole range of saturations required by the properties of the sample and the radially varying centrifugal force occurs within the sample. The calculation procedure nevertheless secures correct results from simply obtained values of the average saturation. The apparatus described was developed in connection with studies of capillary pressure and wetting of oil-field rocks, and the paper provides the apparatus background for a previous publication' dealing more fully with the uses and implications of the data in petroleum engineering. The method is applicable, however, to general combinations of immiscible fluids and porous or comminuted solids, and may be useful in other fields. Introduction The importance of capillary phenomena in determining the behavior of liquids in porous media has long been recognized. The concept of capillary Pressure was early formulated, and in recent Years discussions of the application of the laws of capillarity to oil field problems have appeared.l-3 One reason why progress in the application of capillary phenomena to the solution of problems of reservoir mechanics has not been more rapid has been the lack of a, satisfactory technique for measuring the capillary pressures in reservoir rocks. It is the principal purpose of this paper to describe a method by which the relation between capillary pressure and saturation can be determined for small consolidated core samples which have been extracted and resaturated, Capillary Diaphragm Perhaps the most direct way to measure the capillary pressure in a rock is to make piezometric contact with the wetting liquid through a diaphragm of porous material with high displacement pressure saturated with the liquid in question.3-6 The liquid in the diaphragm assumes the pressure of the liquid in the core, which can then be measured with a manometer, while the atmospheric air is prevented by capillarity from entering the diaphragm and affecting the pressure measurements as long as the displacement pressure of the diaphragm is not exceeded. With an apparatus of the type illustrated schematically in Fig. I, the relation between capillary pressure and saturation can be measured for a small core sample by starting with the core saturated 100 per cent, applyillg successively greater suctions

Jan 1, 1945

By J. K. Stanley

It has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, rema-nence, and coercive force change on cold-working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures—a subject of practical importance in soft magnetic materials—and the other was the feeling that a study of cold-working and strain relief might shed some light onour understandingof what takes place in the deformation of metals. Definition of Terms It is necessary to define the terminology used in this Paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. 1 the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H. (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely demagnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, . Thus u= B/H and if the magnetizing force H (oersteds) is specified as ro or 100 oersteds, the permeability is written as or l00 This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or I00 are chosen as indices for 106

Jan 1, 1945

By George R. Mansfield

INTEREST in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.1 At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,2 some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,3 of the Tennessee Division of Geology. Prof. J. Stewart Williams,4 of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1940

By George W. Bain

SOME problems concomitant with commercial exploitation of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service department wants defects rectified and the cause determined to avoid recurrence. The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character. GEOLOGICAL PROBLEMS The geological problems deal almost exclusively with the size of blocks. Size across the deposit is limited by thickness of individual beds, and along the strike by the space between crosscutting joints. Frequently the vertical depth of a block is reduced by exfoliation shells arising from spontaneous expansion. All these factors require consideration in developing a deposit to fill an order. Thickening of Marble Beds The limestone beds that became the marble deposits of the northern Appalachians and of the Yule locality in Colorado were seldom homo-

Jan 1, 1940

By W. C. Weslow

AN extended program devoted to the development of a matrix for holding diamonds of a size and kind not heretofore generally used is being carried on by the Carboloy Company, and this paper describes the part of the development that affects mining and its allied industries. Laboratory and field work so far has indicated the following: 1. Tungsten carbide and cobalt form the most desirable known matrix material for the holding of diamonds for drilling work. 2. Industrial bort diamonds in sizes and of a class not generally heretofore acceptable and therefore less expensive can be successfully held in this cemented carbide matrix. 3. In exploratory drilling, the combination of bort diamonds, impregnated throughout a matrix of tungsten carbide and cobalt, when fabricated onto drilling crowns, is an indicated economic substitute for drilling crowns in which the diamonds are set by hand, mechanically or by casting. 4. This impregnated type of drilling crown or bit has definite possibilites of revolutionizing the drilling of blast holes, particularly in the harder formations. This will be brought about by the development of high-speed light-weight rotary equipment using an impregnated diamond bit to replace the percussion drill now in general use. (The development of this rotary equipment is well past the laboratory stage at this time.) 5. That the use of a rotary bit is a preventive measure in the fight against silicosis. The development of this product was started by G. F. Taylor at the Research Laboratories of the General Electric Co. It was early recognized that it had possibilities in the drilling field and the present product is the result of considerable experimental work with other powdered metals as well as with tungsten carbide and cobalt. In the study of the potential application to the mining field, it was learned that carbon diamonds originally were given a high rating of performance but that the trend had been toward borts in selected sizes

Jan 1, 1940

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By O. N. Carlson, D. G. Alexander

THE hardness anisotropy of metals and alloys has been of increasing interest in recent years but silicon ferrite,1 niobium,2 and tungsten3,4 are the only bcc metals about which this type of information has been reported. This investigation was carried out on vanadium and chromium single crystals in an effort to determine to what degree the hardness variations observed in these metals are due to orientation effects and to compare their behavior with other bcc metals. In earlier work the authors had observed a small angular dependence in the Diamond Pyramid Hardness of single crystalline vanadium on the (100) plane but no anisotropic effects were noted on either the (110) or (111) planes. At the suggestion of R. G. wheeler5 it was decided to investigate this effect in greater detail using the more asymmetric Knoop indentor. The vanadium metal used in the study was prepared by the aluminothermic reduction of V2O5 followed by electron beam melting.6 The principal analyzed impurities were 230 ppm C, 230 ppm O, 65 ppm N, 90 pprn Al, Cr not detected, 50 ppm Fe, 60 ppm Ni, and 200 ppm Si. The chromium was an iodide-refined product obtained from the Chromalloy Corporation. Analysis of this material showed the following amounts of impurities present: 10 ppm C, 9 ppm O, 2 ppm N, 0.4 ppm H, 3 ppm Al, 2 ppm Ca, 2 ppm Cu, 20 ppm Fe, 1 ppm Mg, 0.3 ppm Mn, 1 ppm Mo, 3 ppm Ni, 10 ppm Si, and 1 ppm V. Single crystals of both metals about 1 cm in diam and 10 cm in length were grown by an arc-zone melt- ing technique.7 The chromium crystal was annealed at 1600°C for 6 hr in a purified argon atmosphere to remove any strains or inhomogeneities, but the vanadium was tested in the as-grown condition. The crystals were oriented by the Laue back-reflection method and then sectioned with a spark cutter into individual specimens with a (loo), (110), or (111) plane parallel to the crystal surface. They were mounted in Lucite and carefully ground to a flat surface. The vanadium specimens were then electropolished in a 6 pct perchloric acid-methanol mixture while the chromium specimens were mechanically polished on a Syntron vibratory polisher using an alumina abrasive. The orientation of each crystal was then rechecked by the back-reflection X-ray method. All of them were found to lie within 2 deg of the desired orientation with the exception of the (110)-Oriented chromium crystal which was within 4 deg. Microhardness impressions were taken at 10 deg intervals from the common (110) direction by rotating the crystal in the plane of the crystal surface. A Knoop indentor was used with a 400-g load on the vanadium crystals and an 800-g load on the chromium. The hardness values are averages of 6 impressions and standard deviations were calculated for each set of data. The values reported for the (111) plane of vanadium are based on from 10 to 15 measurements for each point. The microhardness results for vanadium and chromium are plotted as a function of the angular rotation of the long axis of a Knoop indentor from the (110)

Jan 1, 1970

By B. D. Cullity

This investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy—the thermoelectric efficiency—has been discussed by Telkesl in a recent review of the subject. She gives the thermoelectric efficiency as: W o Efficiency = -Wo ______________i____________ TR-TC+ O2TR-Tc) where W, = power output in external load (watts) Wi = rate of heat input to hot junction (watts) TE,T, = temperature of hot and cold junctions (oA) K1,Kz = thermal conductivity of the two thermocouple materials (watts/cm°C) p,,pz = electrical resistivity of the two thermocouple materials (ohm cm) 9 = thermoelectric power (volts0/C) For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of pfoperties. Bismuth-selenium Alloys work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson who gives the diagram reproduced in There are two intermediate phases in this system, BiSe and Bi²Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedra1 crystal

Jan 1, 1949

By Marcel Schlumberger

The electrical methods for surface-prospecting have been well developed in the last 20 years. The method involves, in the classic form, the sending of an electrical current into the soil, by means of two electrodes A and B, and studying the potential distribution at the surface, by measuring the difference of potential between pairs of points such as M and N. The points M and N are usually placed on a line between, and equidistant from, A and B. By increasing the distance AB, the current sent into the Earth, and likewise the distribution of surface-potentials, become influenced by regions of greater and greater depth below the surface. By varying the form and dimensions of the electrode-arrangements AMNB, called a "quadripole," one may make valuable deductions concerning the nature or thickness of beds, if one knows the electrical properties of these beds. On the other hand, if the form and dimensions of the electrodes AMNB remain fixed, the depth of penetration of currents in the Earth remains, so to speak, almost constant, although it tends to increase where the subsoil is more conductive, and conversely. Therefore, if one moves the constant-dimension quadripole over all the terrain to be Investigated, one achieves approximately a horizontal exploration. This permits a study of tilted beds or faulted horizon-tal beds. When the particular problem becomes deep, of the order of 2000 meters, or more, it is ne-cessary to Increase the distance between the current-sources AB to a length such that the work 'comes very troublesome, especially if the region is wooded. At the same time, the separation the points M and N must be likewise great (for example, one km) in order to obtain differences potential which are not too small; the measurement of potential differences across MN is then difficult because of the presence of parasitic potentials, due to a flow of telluric currents in fourth, and the order of greatness of these currents may exceed the quantities to be measured.

Jan 1, 1940

By Howard A. Meyerhoff

In western Argentina, in the Province of Mendoza and the Territory of Neuquen, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina's limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina's fuel problem. Character of Solid Bitumens The solid bitumens of Mendoza and Neuquen are petroleum derivatives, as is indicated by the following ultimate analysis : Constituents Per Cent Hydrogen.................... 6.8 Carbon...................... 82.4 Nitrogen..................... 1.6 Oxygen...................... 2.7 Sulphur...................... 2.2 Ash.......................... 4.3 100. 0 In physical appearance they bear a close resemblance to coal and are commonly called carbon. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-con-choidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquen. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Es-peranza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1949