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By A. C. Butterworth

M OST operators of open-pit mines in the Lake Superior iron ore district are quite familiar with the use of fuel oil in the heavy-duty Diesel engines commonly used in truck-haulage service but some operators, including my own company, Pickands Mather, have had butane-engine trucks in service for several years, and less is known of their operation. One of the first installations of trucks for iron-ore haulage was in 1939 at a deep open-pit mine on the Cuyuna Range. These superseded standard-gauge steam haulage. Trucks then obtainable were equipped with 150-hp Diesel engines, and the speed of these units on an 8 % grade would have been so slow, considering the depth of the pit, that plans for an all-truck haul out of the pit were rejected. About this time one of the engine manufacturers brought out an auto-

Jan 1, 1948

With only one certain exception coal was never used by the Indians, before white men came to America, for any purpose except as an ornament or for paint. Within the past few years it has been discovered that the Hopi Indians in Navajo County, Arizona, used lignite for burning pottery, about 1000 A. D., as dated by tree rings. They were able to obtain a clear color in their ware that could not be obtained with brushwood fires. The coal was mined by hammers from outcrop openings, some of which can still be seen, and the tools used have been found in them.1 (See also p. 376.) Small figurines made of splint or cannel coal have been found at various localities in western New York, in Ohio and possibly other places, evidently made for ornaments. There is no reason to think they are of any greater age, if as old, as that mentioned above. Some crushed coal was used by the Indians as a black pigment in painting themselves, but apparently the eastern Indians never used coal for any other purposes. Some think that several tribes of Indians in the Northwest, along the Missouri, used coal as fuel, the basis being a statement attributed to Radisson about 1660. In the Jesuit Relations of 1659-1660 it was stated that Radisson anti Groseilliers had just returned from a visit to Lake Superior and beyond. "In the country of the Poualak, which means 'warriors' they say `as wood is scanty in supply and small in size in their country, nature has taught them to make fire with coal from the earth (charbon de terre) and to cover their cabins with skins.'"2 This statement was only hearsay with the good fathers, and the reputation for veracity of the two explorers is not of the best, and it is extremely probable that instead of coal they used turf, dry grass or buffalo chips. In fact in Radisson's Voyages' he does not mention coal at all in his account of the third voyage, when he was supposed to have seen it used. His accounts of his travels are badly mixed, and he and his companions were much better travellers than narrators. None of the early travellers up the Missouri River saw any evidence even then that the Indians were familiar with the use of coal. In the writer's opinion it is unlikely that coal was used as stated by the Jesuits.

Jan 1, 1942

By R. N. Upadhyay, M. Maleki, I. Fatt

Conventional laboratory core analysis tests on samples of two limestone reservoir rocks indicate that about 20 per cent of PV is in dead-end pores. These tests (electric logging formation factor, mercury injection capillary pressure and miscible displacement) were carried out on 1/4-in. diameter test plugs. Test results show a clear dilference between these samples and sandstone or homogeneous limestone reservoir rock. Although the amount of dead-end pore space can be only roughly estimated, the presence of such pore space seems clearly indicated. Pressure transient studies also show presence of deadend PV. Although they do not give quantitative results, pressure transient data yield a reasonable estimate of the size of the neck connecting dead-end pores to the main flow channels. INTRODUCTION Equations conventionally used to describe reservoir flow behavior contain the implicit assumption that all connected pore spaces contributed to both porosity and permeability. Several authors3-7 have pointed out the changes in pressure transient behavior and in electric log interpretation that may result if this assumption is incorrect and, instead, dead-end or cul-de-sac pores are present. There is a need for laboratory tests that can detect presence of dead-end pores in core samples. With such information on hand the petroleum engineer can make more rational use of the mathematical tools now available for analysis of reservoir flow behavior. This paper describes laboratory studies designed to detect and, if possible, give a quantitative measure of dead-end PV in laboratory-size core plugs. Three reservoir rocks were used, two of which were limestones suspected of having deadend pore spaces and a well-known sandstone, used as a comparison standard, in which there is believed to be little or no dead-end pore space. All the studies were designed to measure the natural dead-end PV; i.e., the pore space which is dead-ended because of rock structure. During multiphase flow in a rock without dead-end pores, some parts of one of the phases can become surrounded by the other, thereby giving (for certain flow behavior) an effective dead-end pV8,9. Such behavior will not be described here.

Jan 1, 1967

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

With the exception of the mentions of coal in Illinois in the period 1660-1680, already referred to, the first coal found in the United States was in the James River, Virginia, field. In 1699 a large tract of .land above the present city of Richmond was allotted for a settlement of French Huguenots by the colonial, government, near the present Manakin, about fourteen miles above Richmond. They soon found coal, tradition says it was uncovered by a hunter pulling out a small tree in a. steel) bank near a stream, and Colonel William Byrd, F.R.S., the most prominent man of his day in the colony, wrote to the Colonial Council of Virginia, May 10 and 11, 1701: "The 10th of May, last., I with Coll. Randolph, Capt. Epes, Capt. Webb, &c., went up to the new settlements of ye French Refugees at ye Manaken Town.... We went tip to ye Cole, w'ch is not above a mile and a half from their settlement on the great upper Creeke, w'ch, riseing very high in great Raines hath washed away the Banks that the Coal lyes bare, otherwise it's very deep in the Earth, the land being very high, and near the surface is plenty of Slate.", Some of the Frenchmen were evidently familiar with the use of coal, as on May 22, 1702, "David Menestrier a black smith and one of ye french Refugees Inhabiting at Luciana Petitioning his Excellency that he may have leave to use ye coal mines lately discovered there for his forge his Excellency by and with ye advice of ye Council loth hereby give Leave to ye said David Menestrier to take what coales he shall want. out of ye said Coal mine for ye use of his forge according to ye Prayer of ye said Petition."2 There was some uncertainty about the grant of these lands to the Huguenots which caused the request for leave to use this coal, as a Virginia patent in its usual form allowed the owner to mine all minerals excepting gold and silver, which were subject to royalties for the Crown. After the visit to the coal above mentioned, "Wm. Byrd, understanding the land had not been granted to the French, took out a patent for 344 acres, including the same, (the coal) which patent was dated October 20, 1704".3

Jan 1, 1942

THE following employment items are made available to AIME members on a nonprofit basis by the Engineering Societies Personnel Service, Inc., operating in cooperation with the Four Founder Societies. Local offices of the Personnel Service are at 8 W. 40th St., New York 18; 100 Farnsworth Ave., Detroit; 57 Post St., San Francisco; 84 E. Randolph St., Chicago 1. Applicants should address all mail to the proper key numbers in care of the New York office and include 6c in stamps for forwarding and returning application. The applicant agrees, if placed in a position by means of the Service, to pay the placement fee listed by the Service. AIME members may secure a weekly bulletin of positions available for $3.50 a quarter, $12 a year. MEN AVAILABLE Project Manager or Construction Engineer, 48, married. Twenty-five years' experience on mine, mill and smelter construction work, design and operation, U. S. and Mexico. Speak Spanish. Now employed; available 30 days notice. Prefer U. S. or Mexico. M-698-489-E-1-San Francisco. Mining Geologist, 53, single. Eleven years' intensive field experience giving a completely practical competence for the smallest or largest of areas; plus the highest possible grade of academic background and independent research qualifying for top rating. Available in thirty days or less. Any location acceptable. M-699-3611-E-7-San Francisco.

Jan 1, 1952

W. P. Blake, Shullsburg, Wis.: I desire to express my admiration of Prof. Posepny's memoir, and particularly of the charming manner and spirit of the introduction. With respect to his mention of the ore-deposits of Missouri and Wisconsin, reference may be made to my paper presented at this meeting (Trans., xxii., 621)) showing the existence of dislocations and breaks in the bedding, and their apparent close relation with the localization of the ore-deposits as claimed by Dr. James G. Percival, and also so claimed by Dr. Jenney in his paper before us (Trans., xxii., 171). I have in my paper given reasons for believing that the zinc- and lead-ores in the strata above the compact Trenton limestones were formed by lateral secretion and concentration from above downwards, substantially as shown by Prof. J. D. Whitney, and not by the ascent of solutions through the fissures, as Prof. Posepny (p. 304) seems inclined to believe. In regard to the contemporaneity of the ore and the rocks, and in favor of a later introduction of ore through fault-fissures, Prof. Posepny (p. 310) cites the influence of these fissures. In my paper, already referred to, I have endeavored to show how faults may have influenced the deposition of ore without being themselves channels for the flow of mineral solutions, and how they may have caused the contemporaneous formation of metallic sulphides from sea-water in the body of a forming rock; the faulting fissure being formed at an early period in the foundation rocks, and probably continuing to be a plane of break and movement in the deposits of later formation.

Jan 1, 1894

By Thomas V. Falkie

The use of operation research and computer techniques in the mineral industries continued to gain acceptance during 1966. There are generally at least five sources of information for researchers and practitioners in the field: (1) Technical periodicals like MINING ENGINEER- ING, Mining Congress Journal, etc. (2) Proceedings of the Symposium and Short Course on Computers and Operations Re- search in Mineral Industries, held last year at Penn. State University and jointly sponsored by the University of Arizona, Stanford University, Colorado School of Mines, Penn. State University and the Society of Mining Engineers of AIME. (3) Various local conferences, such as the 1966 Rocky Mountain Minerals Conference held in Denver. (4) United States Bureau of Mines publications. (5) The AIME annual meeting in New York and the SME Fall Meeting in Tampa.

Jan 2, 1967

By Marvin Lee

Kansas continued holding, for its seventh year, the fourth position in the list of oil-producing states. The crude-oil production, according to purchaser's reports to the State Corporation Commission, was 40,008,940 bbl.; as assembled by the Oil and Gas Journal, 41,305,768, and by the U. S. Bureau of Mines, 41,942,000 barrels. Increase of production from 1932 was largely due to greater stability of the industry, and increased return of demand for Kansas oil, caused by the addition of Federal assistance in national production regulation which reduced illegal production, of some areas out of Kansas, that had been destructively competing with Kansas crude or its refined products, at less than cost of production. Prices continued to advance from the lowest level of 25c per barrel during part of May and June, until by the end of September 36" gravity crude had reached $1 per barrel and continued at this price the remainder of the year. Price stability, for a period greater than in previous years, has brought renewed confidence to those producing oil and has led to renewed interest and increased purchases of Kansas leases. Drilling was confined chiefly to the number of wells necessary to protect from offset and other drainage in the field and to meet the requirements of expiring lease contract deeper areas in Mid-Continent, are an added inducement to exploration. The renewal of interest in the search for new fields in Kansas is already apparent and 1934 will probably see more wildcatting than for several years. This is due both to the expiration of leases on large blocks and to actual demand of the industry for new fields. Exploration for favorable areas is being actively conducted by the various methods of surface, subsurface and core drilling and geophysical work. Much of western Kansas cannot be mapped by surface study and geophysical exploration has been of considerable assistance and has led to a large use of the seismograph. Several companies are conducting seismograph surveys and leasing on findings already secured. Development under the more favorable conditions of 1933 can be readily seen by the comparison of the following reports for the last weeks of December in the respective years.

Jan 1, 1934

By Burt A. Waite

The new OSM regulations for ground water monitoring of underground coal mines have been the source of many concerns for the mining industry. Because the regulations were initially written at the federal level, but are being administered at the state level, considerable confusion still exists within the industry as to what is really required. Based on submission and/or approval of more than 30 monitoring plans for existing mines in Pennsylvania, West Virginia, and Ohio, three basic sections are necessary. They are: 1. background data on the hydrogeologic setting of the mine, 2. the monitoring plan itself, and 3. mining procedures to minimize adverse effects on ground water. Like all of the OSM requirements, ground water monitoring will be a new burden the coal industry must bear, but with proper planning and communication with the regulatory authorities it need not be as bad as originally feared.

Jan 1, 1983

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of

By G. J. Heuer, J. N. Dew, G. C. Clark

The effect on well behavior of partial permeability barriers, changes in producing rates and well spacings have been calculated through use of a radial, unsteady-state, two-phase-flow mathematical model. This model allows for variations in permeabilities and porosities with distance from the wellbore. The numerical methods necessary to solve the problem require use of a highspeed digital computer, in this case an IBM 704. In each instance, pressure and saturation gradients, gas-oil ratios and recoveries around a well producing by solution-gas drive have been calculated as a function of time and distance from the wellbore. Comparisons are made to show the effect of changes in producing rate and of varying permeability near the wellbore and out in the formation on the production and pressure history of the well. The effect of different well spacings on producing rate and ultimate recovery is considered. Although the mathematical description of the reservoir is simplified in comparison to an actual reservoir, the results do give some insight into the difficult problem of spacing and proration in a heterogeneous solution-gas-drive reservoir. Results show that for the cases considered spacing has little effect on ultimate recovery and that permeability barriers removed from the well decrease producing rate for a period of time but have only a small effect on ultimate production. INTRODUCTION The effect of spacing and producing rate on the production characteristics and ultimate recovery of a well producing by the solution-gas-drive mechanism have been topics of interest to the oil industry for many years and the subject of many hearings before state regulatory bodies. The problem is very complicated because of the difficulty of simulating in the laboratory a reservoir producing by the solution-gas-drive mechanism under anything like normal field conditions. This paper gives the initial results of a study aimed at determining the effect of these factors on production from reservoirs simulated by a mathematical model. Two-phase, unsteady-state equations are used to calculate pressures, saturations, and rates of oil and gas flow as a function of time and distance from the wellbore. The model is radial, and reservoir properties may be varied with distance from the wellbore. A decrease in permeability at a given distance results in a low-permeability ring concentric with the wellbore through which all the fluids from more distant portions of the reservoir must flow. The current mathematical model allows for variation of permeability, porosity and saturations as a function of distance from the well. Any desired drainage radius for the well may be selected. Drainage radii of 745 and 1,053 ft, which correspond to 40- and 80-acre spacing, were chosen for the calculations which follow. A large amount of the input data has been held constant. No investigation was made into the effect of changes in fluid properties and relative permeability characteristics on oil and gas production behavior. Fluid properties and relative permeabilities are essentially those of the White Mesa portion of the Greater Aneth area in southeastern Utah. A recently concluded hearing before the Utah Oil and Gas Conservation Commission to determine spacing for the field aroused interest in the possible effect of permeability constrictions located some distance from the well on production and recovery. This interest stimulated the present study. In this paper, no attempt has been made to simulate any field production characteristics exactly. Only the solution-gas-drive mechanism has been investigated, and production by liquid expansion has not been considered. This investigation is exploratory in nature but does give some insight into the problems of spacing and proration in a solution-gas-drive field having permeability variations. THE MATHEMATICAL MODEL The mathematical model is similar to that proposed by West, Garvin and Sheldon.' Approximately the same techniques have been used in arriving at a solution. The equations are nonlinear, partial differential equations which have been known for some time. The particular equations used for this study neglect the effects of capillary pressure and gravitational forces. The advent of modern digital computing equipment has made their solution practical. Basically, the method solves for pressure, saturations, and oil and gas flow rates as a function of distance and time. In our model, distance to the

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By Blamey Stevens

(San Francisco Meeting, October, 1911.) My previous paper is entitled, The Laws of Igneous Emanation Pressure. The present paper lays no claim to the exactitude and completeness of a law, since it is of a provisional nature and may be disregarded when experiments have established a basis for more exact reasoning. The general physical states in which aqueous emanations may occur are first considered. The possible physical conditions under which the mineral elements may occur in emanations are then discussed, and a classification of deposits, dependent on emanation, is proposed. A system of scientific experimental investigation is outlined, and it is shown that the physical and chemical properties of emanation may be exactly determined thereby. The investigation is urged as feasible and simple, and not necessarily requiring large and costly apparatus. It is the only step necessary to make possible the formulation of a complete set of laws of igneous emanation. Process of Emanation. In a rising column, magma ranges in temperature from 900° to 1,200°C. Exhalation must begin at some fairly great depth. What this depth may be we can only surmise, since no experimental evidence is available. Exhalation, however, continues as the magma flows upward, until at another level the occluded gases have all escaped. This depth is probably upward of 5,000 ft. (See Fig. 1.) All exhalations must come from between these two levels. As the whole emanation is the sum of the exhalations and residues, the residues must come from below the uppermost level. They will be most abundant when coming, from those parts of the intrusion which have solidified below the lower level.

Apr 1, 1912

DETAILED programs for the Regional Meeting to be held at Boston, on Aug. 29, 30, 31, will be available on arrival at the Copley-Plaza Hotel, where registration will begin at 10 a. m. on Wednesday morning. The opening session will be non-technical in character and will be called to order at 11 a. m. Hector J. Hughes, Dean of the Graduate School of Engineering of Harvard University, and others will speak, and in the afternoon visits are to be made both to Harvard and Massachusetts Institute of Technology. Wednesday afternoon will be devoted mainly to the opening of an exhibit of geophysical instruments and methods at Tech. On the way back to the hotel a tour of Old Boston will permit the visitors to see many of the historic points of the city. A special meeting of the Board of Directors has been called to be preceded by the usual subscription dinner at the University Club at 6.30 p. m. Owing to limita-tions of room, invitations have been sent only to the usual list designated in the By-Laws, the Directors, past officers, chairmen of sections and of technical committees. The dinner and a brief business session of the Board will be followed by a technical session at the Copley-Plaza at 8 p. m. and this in turn by a buffet supper at the University Club at 10 p. m. Sep-arate entertainment is being provided for the women for the evening. Thursday will be devoted to technical sessions both in the morning and afternoon. If necessary to permit adequate discussion, an overflow session will be ar-ranged in the afternoon. In the evening, a subscription dinner will be given at the Copley-Plaza at which past-presidents John Hays Hammond and Robert H. Rich-ards will be guests of honor. It is promised that speeches will be short and dancing will be arranged for following. The women will be offered a luncheon and bridge party at one of the country clubs on Thursday, and Friday will be devoted to an all-day excursion for both men and, women. Members are asked to register promptly on arrival so that the various committees will know as early as possible for how many to provide. The major part of the technical program has been provided by the Committee on Geophysical Methods of Prospecting, and a series of papers of great value and interest in this new field has been brought together. Abstracts of substantially all of them are printed in this issue of MINING AND METALLURGY and the papers themselves will, with one or two exceptions, be avail-able in printed form at the meeting and later in the regular publications of the Institute.

Jan 9, 1928

US 4,134,618-Method for restoring an underground reservoir subsequent to the solution mining of an ore body of uranium, copper, nickel, vanadium, molybdenum, silver, rhenium, or selenium. Clean water a cycled through the mined area, via the injection and production wells used during mining, at a flow rate sufficient to entrain residual dissolved solids. The solids are separated at the surface and disposed of, e g., in a deep disposal well, while clarified water is recycled C A. Kossack, assigned to Atlantic Richfield Co. Jan 16, 1979 4 pp. (299-5) Filed. 12-29-77 (865,646) US 4,155,982-In situ leaching of a subterranean uranium ore deposit The ore is leached with a dilute aqueous solution of ammonium bicarbonate containing a small amount of hydrogen peroxide in order first to convert tetravalent uranium in the ore to the hexavalent state and second to dissolve the hexavalent uranium preferentially to the other metals or elements commonly occurring In such ore The uranium- enriched leach liquor IS brought to the surface, and the uranium recovered by means of adsorption on a particulate ion exchange resin, elution with an acid, and treatment with ammonia to precipitate relatively pure ammonium diuranate. G G. Hunkin, T P. Fife, and J R Stano, assigned to Wyoming Mineral Corp. May 22, 1979. 13 pp (423-7). Filed: 10- 9-74 (51 3,445). Same: Canadian 1,027,849, dated Mar. 14, 1978. US 4,157,847-In the mining of sulfur by the Frasch process hot water accumulating above subterranean sulfur from previous mining operations is recycled downward to contact and heat additional solid subterranean sulfur. Advantageously, pressurized and superheated drive water from above ground is commingled with the underground water to raise its temperature before it is recycled downward R. L Williams, R L Latiolais, J. L Gabriel, and R. L Bouis, assigned to Freeport Minerals Co June 12, 1979. 13 pp (299- 6) Filed 7-28-77 (81 9,879). US 4,158,76%1n this method for determining the uranium content of a solution obtained in the solution mining of an underground uranium ore deposit, the intensity of gamma radiation from the Th-234 daughter of U-238 emitted by the solution is determined as it impinges on a scintillator after being passed successively through filter foils of a ytterbium- tin alloy, a lutecium-tin alloy, and a hafnium-zirconium alloy This scintillation is evaluated as a measure of the uranium content To assure that the uranium-thorium conversion has reached a stable state, the measurement should be made about three months after the uranium solution has been produced R C Smith, assigned to Westinghouse Electric Corp. June 19, 1979 11 pp. (250-255). Filed. 10-20-77 (843,770).

Jan 1, 1980

By Robert J. De Angelis, James H. Barker

An improved method for solving dynawzical dislocation problems using a digital computer is described in this paper. Interactions between two distinct types of dislocations were studied: attractive screw dislocations; and Lomer lock forming dislocations. One dislocation is positioned in the lattice and is initially at rest, while the other dislocation is moved through the lattice on an intersecting slip plane at a constant velocity in the range 0.5 to 0.999C. (C is the transverse velocity of sound.) The results obtained from these computations indicate that screw dislocations account for a small fraction of the total strain over a wide portion of the range of velocities studied. They further indicate that mixed dislocations mainly repel other dislocations in the neighborhood of the active glide plane. From this a possible explanation for cell formation is put forth. The density of Lomer locks expected to exist after a strain of 0.2 was found to be 1.4 x 106 cm-2 which is in good agreement with indirect experimental estimates. IN the past, predictions of favorable or nonfavorable dislocation reactions were based on the associated changes in elastic strain energy. Such considerations take no account of the probability of the two dislocations coming into contact to react. Venables1 was the first to approach these probabilities by considering the interactions between two moving screw dislocations on perpendicular glide planes. Because of the restrictive types of dislocations and glide plane geometry employed, his results have limited application to metallic crystals. The work to be presented here develops a general approach to solving dynamical dislocation problems; either dislocation-dislocation interactions, presented here in detail, or dislocation interactions with any other suitably defined stress field. Two types of dislocation-dislocation interactions common to face centered cubic (fee) materials are considered: those between pure screw dislocations of opposite sign on intersecting slip planes and those between mixed dislocations on intersecting slip planes, that can react to form a perfect dislocation. This latter reaction, referred to as the Lomer reaction, produces a locked product dislocation that finds it energitical favorable to disassociate into two Shockley partials and a stair-rod dislocation. This partial configuration known as a Lomer-Cottrell (L-C) lock plays a major role in work hardening of fee crystals. seeger2 names the L-C lock as the prime contributor to Stage II hardening while Kuhlmann-wilsdorf3 and Meakin and Wils- dorf4 also state that it is a significant contributor to work hardening. However, with a few notable exceptions,5-7 direct observations of the Lomer lock and the L-C lock by electron transmission microscopy are scanty, and even these are subject to other interpretations.5,6 In a study of partial dislocations present in austenitic stainless steel, whelan8 did not observe any L-C locks at the head of pile-up groups. This result contradicted existing work hardening theories and led him to postulate an alternate theory based on the stress required to break away dislocations intersecting a pile-up group, from their stacking fault nodes. Due to the importance of the Lomer reaction in producing L-C locks which are an essential feature in current work hardening theories and because there exist no data giving direct quantitative values for the density of locks, and because there has even been some doubt expressed as to whether this important reaction occurs at all, a study of the dynamic behavior of the mixed dislocations which form the Lomer lock was undertaken. Due to their ability to cross-slip with relative ease, screw dislocations play an important role in the deformation of fee crystals. For this reason, the second type of reaction considered here is between screw dislocations of opposite sign. In addition, computations in volving screw dislocation interactions are relatively simple, thus providing a convenient check on the cornputational scheme employed. DEFINITION OF PROBLEM The force exerted on a dislocation due to a generalized stress field is given by the Peach and Koehler9 equation: Here t2 and b2 are respectively the tangent and Burgers vectors of the dislocation, and T1 is the stress dyadic defining the local stress field. The stress field may be externally applied or generated internally by the presence of a lattice defect, such as a second dislocation, as is the case in this work. Frank10 has shown that an equivalent momentum, P, of a screw dislocation can be defined by: Here, EST is the total energy of a screw dislocation and ESo is its rest energy. The left side of Eq. [2] is the time derivative of momentum and the right side is the position derivative of the energy due to the dynamical nature of the dislocation. The total energy of a dislocation is the sum of the potential and kinetic energies. Weertman11 has developed the expressions which were used here; these give the potential and kinetic energies of uniformly moving edge and screw dislocations in an isotropic medium.

Jan 1, 1969

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900' to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.' Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,' the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-'9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.' In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970