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By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By C. A. Pierce

STUDIES of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its com-mercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft. in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft, of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding for-mations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresses."1

Jan 1, 1938

By Carl A. Zapffe, M. Eleanor Haslem

The present investigation has three principal purposes: 1. To develop a method for measuring hydrogen embrittlement that avoids cer, tain errors complicating previously used methods. 2. To explore in a preliminary way some of the fundamental factors controlling embrittlement. 3. To apply the measurements specifically to stainless grades of steel, whose sensitivity or insensitivity to hydrogen embrittlement has never been clearly defined. Selecting a Test Method Hydrogen embrittlement is a condition of low ductility resulting from excessive absorption of hydrogen by the steel at some period in its history, and may be revealed by almost any test involving cold deformation. Tensile tests, impact tests, and bend tests are commonly used for detecting hydrogen embrittlement; although numerous other tests, such as cold-upsetting or extrusion, could be used. The simplicity of using a wire specimen for cathodic and acid pickling tests, and the especial adaptability of the bend test to wire specimens, led to selection of the bend test for the present research. Bend tests usually have been of three general types: (I) fatigue, (2) reversed bend, and (3) single bend. The first two types, though widely used, are inaccurate because their measurements are counteracted by an aging effect; and the third type has not been developed to its fullest utility. The effect of cold-working in removing hydrogen is well known. During a bend test hydrogen can be observed escaping from the convex side simply by coating the specimen with oil; and any technique employing flexing or reverse bending may therefore have its measurements masked because the mechanical action reduces the embrittlement during the test. This factor is so important that even elastic flexing of a hydrogen-charged wire specimen should be avoided before testing if accurate measurements are desired. Developing a Machine for Measuring Hydrogen Embrittlement As for the single-bend test, its theory is good, and recovery caused by mechanical work is kept to a minimum. With a given degree of hydrogen embrittlement, a specimen will break at a given angle if the bending is applied unidirectionally and uniformly. The radius of the bend must be kept constant; and the rate of bending should be a constant, slow enough to allow reading of the breaking angle, and yet rapid enough to prevent significant recovery from the escape of hydrogen during bending. A simple apparatus (Fig. I) was constructed using a type H Foxboro drive unit A, which is a synchronous motor with a gear-reduction ratio of 600 to I. A cord, fixed at one end to a wooden pulley B on the drive shaft of the motor, follows the pe-

Jan 1, 1947

By Carl A. Zapffe, M. Eleanor Haslem

The present investigation has three principal purposes: 1. To develop a method for measuring hydrogen embrittlement that avoids cer, tain errors complicating previously used methods. 2. To explore in a preliminary way some of the fundamental factors controlling embrittlement. 3. To apply the measurements specifically to stainless grades of steel, whose sensitivity or insensitivity to hydrogen embrittlement has never been clearly defined. Selecting a Test Method Hydrogen embrittlement is a condition of low ductility resulting from excessive absorption of hydrogen by the steel at some period in its history, and may be revealed by almost any test involving cold deformation. Tensile tests, impact tests, and bend tests are commonly used for detecting hydrogen embrittlement; although numerous other tests, such as cold-upsetting or extrusion, could be used. The simplicity of using a wire specimen for cathodic and acid pickling tests, and the especial adaptability of the bend test to wire specimens, led to selection of the bend test for the present research. Bend tests usually have been of three general types: (I) fatigue, (2) reversed bend, and (3) single bend. The first two types, though widely used, are inaccurate because their measurements are counteracted by an aging effect; and the third type has not been developed to its fullest utility. The effect of cold-working in removing hydrogen is well known. During a bend test hydrogen can be observed escaping from the convex side simply by coating the specimen with oil; and any technique employing flexing or reverse bending may therefore have its measurements masked because the mechanical action reduces the embrittlement during the test. This factor is so important that even elastic flexing of a hydrogen-charged wire specimen should be avoided before testing if accurate measurements are desired. Developing a Machine for Measuring Hydrogen Embrittlement As for the single-bend test, its theory is good, and recovery caused by mechanical work is kept to a minimum. With a given degree of hydrogen embrittlement, a specimen will break at a given angle if the bending is applied unidirectionally and uniformly. The radius of the bend must be kept constant; and the rate of bending should be a constant, slow enough to allow reading of the breaking angle, and yet rapid enough to prevent significant recovery from the escape of hydrogen during bending. A simple apparatus (Fig. I) was constructed using a type H Foxboro drive unit A, which is a synchronous motor with a gear-reduction ratio of 600 to I. A cord, fixed at one end to a wooden pulley B on the drive shaft of the motor, follows the pe-

Jan 1, 1947

By David R. Poirier

Activity data of carbon as a function of both temperature and composition throughout the stable austenite range is correlated by mearts of an equation derived from a quasi-chemical model. The carbon activity data of austmite for temperatures between 800° and 1200°C are utilized in conjunction with the activity of carbon calculated for the y solidus using the activity of carbon in liquid iron and published austenite-liquid equilibria. The results agree very well with Chip-man's correlation; however, a small difference in the activity of carbon in the high-temperature range of the austenite field is evident. Excellent agreement is found for the heat of solution of graphite in infinitely dilute austenite; from this study the value is 10,550 cal as compared with Chipman's value of 10,680 cal. AS part of a program to study microsegregation in dendritic solidification of ternary Fe-C-Cr alloys, it was desirable to be able to describe the equilibria between austenite and liquid iron in Fe-C-Cr alloys. In this regard, it was necessary to correlate existing data on the activity of carbon in Fe-C austenite as a function of both temperature and composition. At that time, Chipman's analysis1 of the thermodynamics of binary Fe-C austenite was not available. It will be shown that this study and Chipman's study agree rather well throughout the stable austenite range of temperature and composition; however, some small differences appear at temperatures greater than the eutectic temperature. Benz and Elliott 2 presented isoactivity lines for austenite superimposed on their revised Fe-C phase diagram. Using an expression from Darken and Gury 3 representing Smith's4 activity data between 800" and 1000°C, they found that the activities extrapolated above 1000°C to the solidus did not agree with the activities determined from the corresponding liquidus compositions. It is the purpose of the following argument to reconcile carbon activity data of austenite with the activity in liquid Fe-C alloys as determined by Rist and Chipman. 5 In addition, a simple analytical expression is sought for computational convenience. ACTIVITY DATA OF CARBON IN ZRON Fig. 1 shows the activity of carbon in Fe-C austenite as determined by Smith, 4 Schenck and Kaiser, 6 Scheil et a1.,7 and Bungardt et al.' The lines are merely drawn to separate the data into the respective isotherms. These data are inadequate to determine the activity of carbon at temperatures greater than 1200°C. The activity coefficient in Fe-C liquid alloys was assumed by Rist and chipmans to obey the following

Jan 1, 1969

By J. W. Rutter, K. T. Aust

Competitive growth of recrystallized grains into striated single crystals of zone-refined lead produced preferred orientations of the coincidence type after annealing at 175°C, but not at 300°C. This preferred orientation development was found to result from the higher mobility and lower energy of large -angle coincidence boundaries compared to large-angle noncoincidence boundaries. These mobility and energy difference provide a useful basis for explaining many cases of preferred orientation observed in annealed metals. DURING a study1 of the mobility of grain boundaries in zone refined lead, it was observed that the temperature dependence of the grain boundary migration rate is smaller for large-angle, coincidence-type grain boundaries than for large-angle noncoincidence ("random") boundaries. This observation is illustrated schematically in Fig. 1, which shows log rate of grain boundary migration vs reciprocal absolute temperature for two large-angle boundaries. The upper curve refers to a coincidence-type boundary of the sort discussed by Kronberg and Wilson.2 While the mobilities of these two boundaries are similar at 300°C, the coincidence-type boundary has a greater mobility, by a factor of about: four, at 175°C than does the noncoincidence boundary illustrated in the lower curve. The observation described above suggested a simple experiment for testing the role of grain boundary mobility in the development of preferred orientation in annealed, high-purity lead. On the basis of this observation, it would be expected that if a large number of grains of different orientations are growing competitively, and if relative grain boundary mobility is a controlling factor, then the specimen procluced by boundary migration will contain crystals having random orientations if annealing is done at 300°C, while preferred orientations of

Jan 1, 1962

By Donald L. Katz, Leo B. Bicher

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By Leo B. Bicher, Donald L. Katz

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

W. Morton Webb, Germiston, Transvaal, South Africa (communication to the Secretary*):—The experience of Mr. Boeh-mer in the Leadville district and his reputation as an engineer assure the interest of anything he may write on the ore-bodies of that district; and all engineers who have operated in Leadville will agree that the theory of the origin of the Leadville deposits, as given by Mr. Emmons in his famous monograph, does not adequately explain the genesis of all the deposits. The solutiou of the problem does not, however, appear to be quite so simple as Mr. Boehmer would make it; and the advance pamphlet issued by the U. S. Geological Survey, pending the completion of the main report, shows that there is still much ground for controversy. No doubt the later eruptive0 had a greater influence on the deposition of the ore-bodies than was thought at the time of the first investigation by the Survey; but it has always appeared to me that the influence exerted by these dikes mas more in the nature of a physical than a chemical one. The weight of evidence in recent years is mostly in the direction of ascension rather than lateral secretion; and one of the strongest evidences is the fact that most of the ore-bodies lie under one of the comparatively impervious layers which help to make up the structure of these hills.

Jan 1, 1911

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By J. W. Hickman

INTRODUCTION RECENT work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of. these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution-type over-the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions.1 In. order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where Cu+ is 0.96Å and Ni-++ is 0.70Å, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with electrons. This composition in the copper-nickel alloys corresponds to 40 at. Pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is filled at 6o at. pct copper or 4o at. pct nickel. Mott and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel -has the-configuration: 3d8 4s2 and copper: 3 d10 4s) then at 60 at. pct copper or 4o at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may' exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. SURVEY OF LITERATURE The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1948

By H. A. Kendall, W. C. Goins

Several investigations in recent years have shown that drilling rates are increased significantly with increased hydraulic horsepower. But, there has been no over-all method of designing jet-bit programs that efficiently uses the surface power. A study of present practices indicates that frequently as little as 50 per cent of the possible effects at the bit are used. Some observers have indicated that the best utilization of hydraulic horsepower (maximum effect on drilling rate) occurs when the bit hydraulic horsepower is maximum; others have stated that jet impact force is more important, and others have believed that maximum jet velocity is required. Limited efforts to date have shown some optimum conditions for bit hydraulic horsepower and impact, but these conditions cannot exist during drilling of a large part of the hole and do not provide a basis for designing a complete jet-bit program. This paper shows the maximum obtainable bit horsepower, impact force and jet velocity at all depths, taking into account the limitations of the pump, piping, hole and minimum circulating rate for adequate cuttings removal. Ranges of operation are developed; and flow rates, surface pressure and bit pressures are specified for each range to provide a maximum of any one of the desired effects. It also is shown that, by proper selection of nozzle sizes and by following the rules presented, the maximum obtainable quantities can be effectively utilized from surface to total depth. Finally, a simple graphical method of selecting nozzle sizes and flow rates is presented which can be used with familiar bit-company hydraulic tables and calculators to design jet-bit programs for maximum bit hydraulic horsepower, impact or jet velocity, as desired. These programs make most effective use of the pumps. Heretofore, there was no method available for designing field tests which adequately separated the effects of bit horsepower, impact and jet velocity. The programs and procedures developed in the paper are dissimilar and, when used in future field testing, should demonstrate which program is the most important in obtaining the fastest drilling rate. INTRODUCTION During the past decade, rig hydraulics has come into increasing prominence. There has been a definite trend toward providing higher horsepower pumps, jet-type bits have had increased use, numerous investigators"" have reported increased drilling rates as a result of increased hydraulics, and bit manufacturers have provided tablesa-" and calculators that are now commonly used 10 design jet-bit programs. Opinion has varied as to the hydraulic quantity which has the great- est effect on drilling rate. Papers and data have been presented that show pump horsepower,'9 it hydraulic horsepower and jet impact force,' each to be the most significant factor affecting drilling rate. Examinatibn of jet-bit programs of the bit companies indicates emphasis on jet velocity. Only pump horsepower can be eliminated because it can be used to produce any one of the bit effects which, a priori, must be more relevant factors. This contradictory state of opinion and practice regarding the bit effects is unfortunate, but several published references have been concerned with making one or another of the factors maximum; and, because these in each case have given results applicable to only intervals of the hole drilled, there seems to be ample reason to complete the previous efforts. It also is believed that the differences in programs for each effect, where they exist, should be delineated so that future use may determine which hydraulic effect is the more relevant. It is the purpose of this paper to: (1) show the theoretical maximum bit hydraulic horsepower, jet impact force and jet velocity available at all depths, taking into consideration all necessary restrictions on operating conditions; (2) illustrate procedures by which the maximum available horsepower, impact force or veIocity may be obtained; and (3) present a graphical method for rapid selection of jet-nozzle sizes and flow rates to be used with conventional procedures to design jet-bit programs for maximum bit horsepower, impact force or velocity as desired.

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By Toshihisa Adachi, Shosei Serata, Shunsuke Sakurai

The present state of knowledge of three-dimensional rock properties does not provide an adequate basis for evaluating the safety of under- ground structures in situ. Most of the triaxial studies reported in the past have dealt with crushing strength, but have failed to consider the intergranular behavior and triaxial strain state of rocks. Without this information, the structural competence of rocks cannot be accurately assessed. The absolute three-dimensional testing method (ATT) was conceived for the purpose of analyzing the three-dimensional states of stresses and strains in aggregate rocks under conditions commonly encountered in underground structures. In-situ stress-strain states are not simple, even in the simplest possible form of opening, excavated in a homogeneous and isotropic rock medium. In general, there are four basic stress-strain states which are present in underground openings, regardless of the complexity of their geological conditions. They are the yielded, brittle-fractured, stress-relieved, stress-concentrated states, as illustrated in the schematic diagram, Fig. 1. The ATT machine was designed to create and study all these states in the laboratory. A theory describing the aggregate behavior of rocks under these diversified states is essential to evaluate the safety of underground structures. The Griffith theory is limited to tensile failure of ductile materials and therefore does not apply to behavior of aggregate rocks under compression. The Griffith theory also fails to consider the grain boundary characteristics of aggregates, which is the determining factor of rock behavior. The Mohr-Coulomb theory of failure ignores the importance of the intergranular behavior of rocks. An application of the continuum theory to

Jan 1, 1972

By Robert L. Llewellyn

Preparation of coal begins at the face in underground mines or in the pit with surface mines. Impurities in raw coal can be in the seam itself or in extraneous material taken in mining from the roof or bottom. Raw coal is prepared only to the extent that is necessary to make the product salable. Over 60% of all coal production is processed to some extent in cleaning plants. For underground mines the proportion cleaned is 72% as compared to 42% from surface and 15% from auger mines. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only as necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent and only incidently with mines shipping raw run-of-mine coal crushed to a top size of, usually, 2 to 4 in., with little, if any, other treatment. ECONOMICS OF COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-rang planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and atomic energy. Cod prices for power plants are still on a Btu (British thermal unit) basis but with more emphasis on sulfur content. For metallurgical coal, the lower and medium volatile coals are in demand and the price rises, generally, as the volatile percentage is lower. Moisture affects the Btu value of coal almost the same as ash content, but dusty conditions during loading and unloading are no longer accept-

Jan 1, 1973

By G. Rowan, M. W. Clegg

Approximate analytical solutions for non-Darcy radial gas flow are derived for bounded and infinite reservoirs producing at either constant rate or constant pressure. These analytical solutions are compared with published results for non-Darcy flow obtained on digital and analogue computers, and the agreement is show to be very good. Some observations on the interpretation of gas well tests are made. INTRODUCTION The flow of gases in porous media is a problem that has been the subject of much study in recent years [l - 71 , and many methods have been proposed for solving the non-linear equations associated with it. The assumption that the flow satisfies Darcy&apos;s Law It has been observed, however, that the linear relationship between the flow rate and pressure gradient is only approximately valid even at low flow rates, and that as the flow rate increases the deviations from linearity also increase. It has been suggested by a number of authors that Darcy&apos;s Law should be replaced by a quadratic flow law of the form This form of equation was first suggested by Forchheimer [9] and, later, Katz and Cornell [10], and Irmay [lll, developed a similar equation. Houpeurt [12] derived this form of equation using the concept of an idealised pore system in which each channel consists of sequences of truncated cones giving rise to successive restrictive orifices along the channel. This type of representation leads to a quadratic flow law of type [4], for all fluids, but it is found that the quadratic term is only significant in the case of gas flow. The methods of Houpeurt for solving gas flow problems will be discussed further in another section of this paper. Solutions of the non-linear equation for Darcy gas flow 121 may be classified as either computer (digital and analogue), or approximate analytical ones. The former include the well-known solutions of Bruce et al. [13], and Aronofsky and Jenkins [14] , but the latter solutions, apart from the simple linearisation of equation (2) to yield a diffusion equation in p2 , are not so well-known. Amongst these approximate analytical solutions should be mentioned the work of Barenblatt [IS], who has applied the techniques of dimensional analysis to obtain similarity solution to a large class of non-linear equations; also, a number of Russian authors, including Barenblatt [16] , Kim [17] and others, who have used the method of moments for obtain-

Jan 1, 1965

By Pol Duwez, Spencer R. Baen

A LTHOUGH the practical importance of Fe-Cr--iV Mo alloys has long been recognized, constitution studies have been limited to a few alloys within rather narrow ranges of composition. The purpose of the present study was to establish the phase boundaries in the ternary diagram at a temperature of 1200°F (650°C).* The identification of phases and the determination of phase boundaries were based primarily on X-ray diffraction measurements and occasionally on microscopic observation. The methods used for locating the phase boundaries were essentially those described in detail by Andersen and Jette,&apos; and by others.&apos;, The compositions of 180 alloys, prepared by powder metallurgy techniques, are shown in Fig. 1. The chemical analysis and mesh size of the powders which were used for the preparation of the alloys are given in Table I. The powders were mixed for 48 hr or longer, then compacted under 80,000 psi in a %-in. diam steel die. Each specimen weighed approximately 5 g. The compacts were sintered for 4 hr at 2500°F (1371°C) in an atmosphere of pure dry hydrogen (dew point near the temperature of liquid nitrogen). An open tray of chromium powder was placed upstream of the compacts to act as a "getter" for the last traces of oxygen or water vapor. In many cases this chromium powder was bright after sintering. Occasionally the upstream side of the powder was slightly greenish, but in all cases the downstream side was metallic. Some of the alloys contracted during sintering and some expanded as much as 20 pct. The latter alloys, which in all cases were brittle, were crushed in a tool steel mortar, repressed, and resintered for 4 hr at 2500°F. After sintering, the alloys were aged for ten days at 1200°F (650°C) in evacuated (105 mm Hg or better) fused silica tubes and were cooled rapidly to room temperature following the aging treatment. The use of the powder metallurgy technique in preparing alloys for structural investigation offers a simple method &apos;of avoiding contamination or non-homogeniety which could result from a melting operation. It is very often possible to dispense with chemical analysis of the alloys which have been prepared by the powder metallurgy method. In lieu of chemical analysis, it is necessary to determine the weight of the compact before and after sintering. The chemical composition of the alloy may be considered as that of the green compact, within the limits of accuracy determined by the loss of weight during sintering. In phase-diagram studies it is important to achieve homogeniety in structure, whether the alloys are prepared by powder metallurgy or by melting. Homogeniety means complete diffusion during the sintering of the alloys which are prepared by powder metallurgy. It has been found from experience that the best criterion for establishing the completeness of diffusion is the sharpness of the X-ray diffraction patterns. This criterion has been used throughout the present study. The X-ray diffraction data were obtained using powder cameras of either 214.86 or 71.62 mm diam. Copper, cobalt, or chromium Ka. radiation was used, the choice being based on the alloy composition. The powder samples were obtained by filing or crushing, depending on whether the alloy was ductile or brittle. In some cases, the powder was annealed for 4 to 6 hr at 1200°F in vacuum. The measurements were corrected for film shrinkage and absorption. The large camera, in which the film is mounted

Jan 1, 1952

By Francis R. Conley, John A. Sievert, John N. Dew

A brief review is presented of the past performance of a number of large, thin, highly permeable reservoirs with low dips in the Bolivar Coastal fields of Venezuela. The performance of these reservoirs indicates that the fluids are segregated vertically within the sand section by gravity. With this assumption, equations are developed which describe the performance under pressure maintenance operations. Methods of solving these equations and results of simple example calculations are presented. Example calculations indicate that under pressure maintenance conditions injected gas tends to {tow preferentially along the top of the sands and that encroaching water has a tendency to flow preferentially along the bottom. The expected performance of segregated fluids is discussed and compared with that of fluids which are uniformly distributed in any sand section. INTRODUCTION The field performance of a number of reservoirs described herein indicates that the fluids are segregated vertically within the sand section by the force of gravity. Thus, it was felt that any method used to predict the future performance of these reservoirs should consider the effects of segregation in the sand sections. A study of the available information on some of the reservoirs suggests that increased recoveries may be expected if the reservoir pressure is maintained by either crestal gas injection or flank water injection. To predict future performance of reservoirs under pressure maintenance operations, a method of analysis was needed which would account for segregation of fluids in the sand sections. Several methods of analysis have been developed to take into account the segregation of fluids in the reservoir as a whole1,3 To our knowledge no method considers segregation of the fluids within sand sections in the manner indicated by the past performance of several reservoirs in the Mara-caibo Basin. This paper outlines part of the work done in studying some of these reservoirs and contains a description of their performance characteristics. The analysis presented is restricted to pressure maintenance conditions, since space limitations prevent a full discus- sion of the development of the mathematical relations and the various methods of solving them. Only a sketch of the development of the mathematical relations is given. The various methods of solving these relations are pointed out, but the actual determination of solutions to various problems are omitted except for one example. It is felt that these results may aid in the study of reservoirs outside the Maracaibo Basin. Some concepts on which the present analysis is based are outlined by D. N. Dietz. However, the analysis presented herein includes several factors not considered by Dietz: (1) variations in permeability and in the cross section, (2) various shapes of the cross section, and (3) the production of fluids. Also, the mathematical development presented by Dietz differs considerably from our corresponding analysis. RESERVOIR CHARACTERISTICS The reservoirs under consideration, large and thin, with low dip and high permeability, are large to the extent that they contain from 0.5 to over four billion bbl of oil initially in place. The section thicknesses vary from 100 to 400 ft and the lengths from 10,000 to 40,000 ft. Thus, a length-wise cross section of the producing formation appears to be long and thin. The dip angles vary from 0 to 6 degrees and the average permeabilities vary from 0.5 to over three darcies. The reservoirs contain from 20 to 50 per cent shale inter-laminated with the productive sands. Most shale breaks within the major sands do not correlate from one well to the next, and correlation is often difficult, even between wells drilled from the same location. However, it is often possible to correlate the shale breaks between major sands for some distance. Herein we are concerned with the performance of reservoirs containing oil of gravities over 20" API. Past reservoir performance indicates good pressure communication and, in cases where pressure sinks have developed, large amounts of fluid migration have occurred. Few of the reservoirs have had initial gas caps, but also, few have been found to be highly under-saturated. Due to gravity segregation, secondary gas caps usually form before the pressure has been reduced more than 25 per cent of its initial value. The effect of gravity has not only been apparent on a reservoir-wide basis, but has also caused segregation of the reservoir fluids in productive sections. Proof of this is found from the results of selective well tests, workovers, and electric and various other types of logs. Evidence that

By Gregory L. Gullord

In September, 1975, production was begun at the new milling facility of ASARCO Incorporated, the Young Mill. The mill is located adjacent to the Young Mine 35 km (22 miles) east of Knoxville, Tennessee. The Young Mill replaced the obsolete Mascot Mill which had been operating since 1913. The basic flow sheet of Mascot was retained for the construction of the Young Mill, with a 20% increase in capacity included in the design. The Young Mill is capable of processing 7710 - t/d (8500 stpd) of crude ore from three underground mines (Young, Immel and Coy) yielding 300 - t/d (330 stpd) of 63% zinc concentrate. The Young Mill is unique in that 92.5% of the ore milled is recovered as saleable products, including zinc concentrate, construction aggregate, sand and agricultural limestone. Processing at the Young Mill is divided into five basic stages: two-stage crushing, heavy media separation, grinding-flotation, concentrate filtering and drying, and limestone by-products recovery. The ore bodies are located in the Knox formation, which consists of primary dolomite, secondary dolomite and limestone with silicas in the form of chert and jasperoid. The zinc mineralization occurs as an exceptionally pure sphalerite. The ore contains an occasional abundance of pyrite and traces of fluorite and barite. TWO STAGE CRUSHING Ore enters the crushing section from two points. The Young Mine ore is hoisted into a 816 ton (900 st) bin which feeds a 1.52m (60 in) conveyor via a 1.52 m (60 in) vibrating feeder. The Immel ore is trucked 10 km (6 miles) by an independent contractor and weighed on automatic recording truck scales at the entrance to the property.

Jan 1, 1977