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In the examination of an undeveloped prospect a decision must be arrived at from an inspection of the outcrops and the exposures in a few shallow pits. Prospects that are offered for sale rarely expose any important quantity of good ore, work having usually been stopped when the immediate exploration no longer yielded favorable results. It should be borne in mind, furthermore, that a great majority of prospects have been examined many times, and if of conspicuous promise, would have been acquired-for development. In most cases the problem for the engineer, therefore, is to discover the traces of a valuable mineralization that has disappeared through solution, or the conditions that indicate the possibility, or probability, of underlying secondary enrichments. The available data being meager, every feature should be the subject of careful study-the condition of the outcrop, the structural relationships, the associations of minerals, the alterations of wall rocks, the chances for underlying enrichments, and so forth, as well as the actual assay value of the material exposed. It is frequently advisable to spend the time and money necessary to have trenches dug at various significant points along a promising outcrop; such exposures, even if the depth attained is slight, often disclose conditions that are not apparent at the actual surface, as for example, the existence of soft minerals and the distribution of the various minerals through the mass of the deposit. Trenches also permit samples to be taken from points that were not accessible during former examinations. Strong, persistent outcrops of uniform width may be taken to indicate the probable size and character of the underlying vein,

Jan 1, 1932

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By J. S. Owens, R. W. Marsden, J. W. Emanuelson, R. F. Werner, N. E. Walker

The iron ores of the Mesabi Range occur in a 340 to 750-foot thick, Precambrian cherty iron formation termed "taconite." For about 65 years, extensive natural iron ore bodies were mined, and the ores either shipped as a direct ore or processed by gravity methods to a shipping grade iron ore. Since 1956, magnetite taconite ores, occurring in magnetite-rich horizons in the Biwabik iron formation, have been commercially concentrated and agglomerated. The transition from natural ores to concentrating-grade ores is progressing rapidly so that, in the near future, a major percentage of the iron ore shipped from the Mesabi Range will be as iron ore pellets produced from taconite. Natural iron ores of the Mesabi Range occur in the Biwabik formation as trough ore bodies in elongated channels and as irregular and tabular deposits in fractured areas associated with faults and folds. Ore bodies range in size from a few thousand tons to hundreds of millions of tons and may occur in any part of the iron formation. In some areas of strong ore development, ore was formed from the hanging-wall argillite to the footwall quartzite. The natural ores and beneficiating-grade natural crude ores were formed by the oxidation of the iron minerals, magnetite, greenalite, stilpnomelane, minnesotaite, and siderite, to hematite and goethite and by the removal of much of the silica in the cherty quartz and in the associated silicates by leaching. The ores are believed to have formed by the oxidizing and leaching action of surface waters. Magnetite taconite ores occur as stratigraphic zones in the Biwabik formation where it contains sufficient magnetite to be concentrated profitably, by magnetic methods, to give a magnetite concentrate that is agglomerated into a high quality product. Unoxidized taconite has an extensive distribution away from and between channels of oxidation and leaching but only a part of the unoxidized taconite is of ore grade. Two general types of magnetite taconite ore occur: ( 1) magnetite taconite of the Main Mesabi Range, generally west of Mesaba, which is composed of magnetite associated with cherty quartz, greenalite, stilpnomelane, minnesotaite, and carbonates and (2) magnetite taconite of the Eastern Mesabi, generally east of Mesaba, composed of magnetite associated with quartz, cummingtonite, actinolite, ferrohypersthene, hedenbergite, fayalite, hornblende, pyroxene, garnet, and biotite. The Mesabi taconite is a metasediment derived from an iron- and silica-rich chemical sediment that has been regionally metamorphosed and, on the eastern end, additionally metamorphosed by the Duluth Gabbro Complex.

Jan 1, 1968

By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By D. L. Marshall, O. F. Thornton

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By Bernard S. Borie

THE U-A1 binary system has been studied by Kaufmann and Gordon.' They have shown that three intermetallic compounds occur in the system: UAl², UAl², and a third compound tentatively identified as UA15. UA1³ is simple cubic, a, = 4.26A. Its unit cell contains one formula weight, and it is iso-morphous with AuCu³. UA1² is face-centered cubic, a, = 7.72A, with eight formula weights per unit cell. Rundle and Wilson have shown that it is iso-morphous with Cu²Mg.² A Debye-Scherrer pattern of the Al-rich compound indicated a more complex structure than either UA1² or UA1³. The following is a report of an investigation of the crystal structure of this compound and a determination of its stoi-chiometric formula. A melt of uranium (99.9 pct pure) and aluminum (99.9 pct pure) was prepared which contained about 25 pct U by weight. It was cooled from 950" to 650°C at a rate of 500" per hr and then taken from the furnace and air cooled. An X-ray diffraction pattern of the ingot showed only lines of aluminum and the Al-rich compound. Filings from the ingot were reacted with a solution of sodium hydroxide, producing a fine black powder, the diffraction pattern of which showed no traces of aluminum. A comparison of the Debye-Scherrer pattern of our sample with the data published by Kaufmann and Gordon1 showed that it is identical with the Al-rich phase which they reported. Single crystals were obtained by cooling the melt more slowly (about 50°C per hr). After reaction with sodium hydroxide, the crystals appeared as small black needles attached to the ingot surface. Cell Size, Space Group, and Uranium Positions A series of Weissenberg photographs for rotation about two of the crystallographic axes, taken with copper radiation filtered through nickel foil, revealed an orthorhombic cell of dimensions: a = 4.41 ± 0.02A b = 6.27 ± 0.02A c = 13.71 ± 0.03A Reflections of the type hkl were observed only if: h + k + I = 2n, of the type hkO only if: h = 2n and k = 2n, of the type h01 only if: h + 1 = 2n, and of the type Okl only if: k + 1=2n. Hence, the cell is body-centered with an 001 glide plane. The evidence for the existence of the glide plane is the observed extinction of 23 possible re- flections of the type hkO with at least one index odd. There are only two space groups consistent with these data: C"" — I2ma and D28 2h — Imma.³ he possible sets of atomic positions for these space groups are: 12ma: (0 0 0; ½ ½ ½) + 4: (a) x 0 %; x % % (b) x ¼ z; x ¾ Z 8: (c) x y z; x y z; x, ½ + y, Z x, M - y, z Imma: (0 0 0; ½ ½ ½) + 4: (a) 0 0 0; 0 ½ 0 (b) 0 0 ½; 0 ½ ½ (c) ¼ ¼ ¼; ¾ ¼ ¼ (d) ¼ ¾ ¾ ; ¾ ¾ % (e) 0 ¾ Z; 0 ¾ z 8: (f) x 0 0; x 0 0; x 1/2 0; x ½ 0 (g) ¼ Y ¼; ¾ Y ¾; ¾ y ¼; 1 y ¼ (h) 0 y z; 0; ;; 0, ½ + y, z; 0, l/2 - Y, Z (i) x 1/4 z; x ¾ z; ¼ z; x ¾ z 16: (j) xy z; x y z; x y z; x y z; x, ½ + y, Z; x,½ - y, z; x, ½ - y, z; 11 1, + y,Z Though density measurements on different samples were found to vary somewhat, they were all within the range 5.7 * 0.3 g per cu cm. If it is assumed that the unit cell contains four formula weights of UAl,, it is 6.5 g per cu cm. If there were as many as eight uranium atoms per unit cell, the

Jan 1, 1952

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By W. Rostoker, A. Siede

THE venerable problem of hydrogen embrittlement of ferritic iron lacks as yet a complete explanation. Possibly part of the difficulty has been the exclusive preoccupation with the total ductility prior to fracture. In the past few years it has been noted at least twice1,2 that hydrogen charged into iron has the ability to depress the upper yield point and, at room temperature, to eliminate completely the discontinuous yield phenomenon. Cracknell and Petchl rationalize that the depression of the yield stress is an example of the behavior of inhomogeneous stresses. Their explanation requires that microcracks exist in the annealed metal, and that hydrogen collect in these cavities under high hydrostatic pressure. The hydrostatic pressure of hydrogen generates localized tensile stresses in the iron which, with external loading, reach the critical stress for yield prematurely. The local plastic zones will spread across the specimen before the Lüders bands can be generated, and the yield-point elongation phenomenon is eliminated. This viewpoint will be discussed in succeeding paragraphs. Rogers,2 on the other hand, represents the depression of the initial flow stress as a result of the interaction of hydrogen with dislocations. He submits two alternative modes of interaction. In the

Jan 1, 1959

By M. J. Blackburn

The phasal equilibria in TI':Al alloys has been studied Ry transmission electron microscopy, electron diffraction, and X-ray diffraction. It is shown that three-phase fields exist below the transformation, viz.: a disordered hexagonal solid solution a; an ordered hexagonal phase based on Ti3Al, aa; and a two-phase region. (a + (YZ) , occurring between the single-plzuse fields. The size. disiribution, and morphology of- the a, phase in the two-phase region is shown to be dependent upon the alloy composition and heat treatement. The ordering process in the a, phase leads to the formation of anliphase domain boundary networks; the contrast and stability of these networks is shown to be dependent on alloy composition. A new and relatively simple phase diagralil for the systemm is constructed. The phasal equilibrium at the titanium-rich end of the Ti:Al system has long been the subject of considerable controversy. crossleyl has recently reviewed the phase diagrams that have been advanced for the system and in his turn proposed yet another one. There would seem to be general agreement that a phase exists at a composition at or near Ti& with an ordered hexagonal DO,,-type structure. However, several other phases have been proposed; for instance, Ence and ~ar~olin's' diagram includes two phases, Ti2A1 and Ti3A1, in the region up to 25 at. pct Al. The position of the proposed phase boundaries varies over a considerable compositional and temperature range, a point graphically illustrated in Fig. 1 of Crossley's paper.' It is perhaps germane to briefly examine the techniques used by other workers in the establishment of the phase structure. These fall into three categories: 1) X-ray diffraction, the only limitation of which is the rather low intensity of superlattice reflections in this system.3 Thus, superlattice reflections become increasingly difficult to detect in the more dilute aluminum alloys. 2) A considerable amount of optical microscopy has been performed"2'4 and it will be shown in a later section that many of the obscure mi-crostructures that have been observed can be attributed to hydrogen contamination. It is concluded, therefore, that such observations should be interpreted with considerable care. 3) The variation of some physical property with aluminum content has been measured.5"7 These methods are a useful indication of the existence of a transformation, but are usually insufficient in themselves to identify the transformation. The results using these techniques will be considered in more detail in the discussion. In this paper, the phase structure of alloys containing up to 25 at. pct A1 has been studied by transmission electron microscopy and X-ray techniques, and the results are used to generate a new and relatively simple diagram for the titanium-rich end of the Ti:Al system. EXPERIMENTAL A series of alloys containing 5.05, 10.16, 13.39, 13.99, 14.40, 20.83, and 25.05 at. pct A1 were obtained in the form of hot-rolled sheet 0.02 in. thick. These alloys contained 0.10 to 0.15 pct 0. Thirty-gram arc-melted buttons were prepared from iodide titanium and 99.99 A1 which contained 16.1, 16.9, 18.2, 19.0, 21.6, 22.2, 23.0, and 23.9 at. pct A1 and had an average oxygen content of 0.03 pct 0. The differences in oxygen content did not appear to influence the nature of the phase transformations which were found. Oxygen content may affect the temperature of these transformations, but insufficient samples of the high-purity alloys were examined to answer this question. The heat treatment of alloys was performed in dynamic atmosphere and vacuum furnaces or in helium -filled silica capsules. A special vacuum furnace was constructed to provide a high quenching rate in which rates of 4000°C per sec were obtained using water as the quenching medium. As pointed out by Crossley,' it is important to avoid heat treatment in the a - [} phase field as the resultant segregation of the alloy into the two phases containing different amounts of aluminum can persist through subsequent treatments leading to ambiguous results. It will be demonstrated later that step cooling of specimens from the a phase region can also lead to anomalous effects. Thus, all solution treatments were carried out in either the a or 3 phase fields followed by water quenching and subsequent isothermal annealing at various temperatures. X-ray analyses were performed on a diffractometer on fine-grained bulk specimens. The value of long-range order parameter, S, wa_s calculated from the integrated intensity of the (1211) reflection. In general, the intensity of the (1011) superlattice reflection was compared with that of the (2021) fundamental reflection to correct for experimental differences between measurements. Thin foils for electron microscopical examination were produced by electropolishing using the technique described in an earlier paper.8 Dark-field techniques were employed to a large degree in this investigation using the gun-tilt method. Finally it should be noted that the lattice parameters of the D01,-type superlattice are approximately related to the disordered hexagonal phase parameters by Crf - c, and 2ad - a, where the subscripts s and d refer to the ordered and disordered unit cells, respectively.

Jan 1, 1968

By J. K. Kerver, J. S. Osoba, J. G. Richardson, J. A. Hafford

A detailed study of a number of methods of relative permea-abilitv measurement has been made in a search for the tech-niqrle most suited to routine analysis of cores taken from reservoir rock. It has been found from tests run on the same samples of core material by a number of techniques that the Penn State, Hassler, Hafford, and dispersed feed techniques all yield results which are felt to be reliable. Conditions under which the faster single core dynamic technique may be used are described. Further work on the calculation of relative permeabilities to oil from data obtained by the gas drive method is needed before this latter rapid method can be utilized. Correlations between theoretical studies and experimental results have been obtained in studies of the boundary effect. pressure distribution in two-phase flow, and gas expansion effects. Previous conclusions that the effects of the outflow boundary could be made negligibly small have been substantiated. Results of experimentally determined oil and gas pressure distributions along a core sample during flow are presented. Further studies of the effects of rate of flow in the measurement of relative permeability-saturation relations have shown that results are independent of the rate of flow as long as the flow rate is below the point where inertial effects commence. An analysis of the effects of a severalfold expansion of gas along the flow path indicates that while saturation gradients are induced in the test sample, the errors caused by this phenomenon in relative permeability measurements are small. INTRODUCTION Many pages of literature have been devoted to pointing out the need for relative permeability-saturation relations in reservoir engineering. One of the most attractive ways of obtaining this information is by the analysis of samples of core material taken from the formation in question, and again literature has described man); methods for obtaining these data. It is the purpose of this paper to present the work that has been done in the study of some of these published methods together with some other methods that have been recently developed in this laboratory. Also, a study of some of the factors that influence the laburatory determination of relative permeability-saturation relations is presented. FACTORS WHICH AFFECT LABORATORY STUDY OF FLUID FLOW THROUGH RESERVOIR ROCK To determine relative permeability-saturation relations of samples of reservoir rock in the laboratory, it is important to know what factors affect these measurements in order that the magnitude of these effects can be ascertained and steps then can be taken to eliminate or, in some cases, to minimize them. The factors that have been investigated are the boundary effect, the effect of gas expansion. and the rate effect. Boundary Effect In laboratory experiments in which two immiscible fluids are flowed through a porous medium, there exists a discontinuity of capillary properties at the outflow face. This discontinuity exists became the fluids pass from a region of finite capillary pressure in the sample to a region of zero capillary pressure in an open receiving vessel. The capillary forces existing in the core caupe the rock to tend to retain

Jan 1, 1952

By D. E. Etter, J. E. Selle

The Pu-Ce phase diagram was determined by differential thermal analysis, metallography, and elechm-nricroprobe analysis. The dingram is chararterized by a eutectic with extensive solid solubility in the cubic Phases of both cerium and plutonium. No intermediate phases were found. Cerium is soluble in e plutonium to 16.0 at. pet Ce at 626OC nnd in d plcltoniurn to 23.0 at. pet at 613 "C, decreasing to 17.5 at. pet at room temperature. No solubility in the a, ß, or ? phases was jound, and the mininum cerium required to stabilize 5 plutonium to room temperature is 3.2 at. pet. The maximum solubility of plutonium in 6 cerium is 19.5 at. pet at 721OC, and the maximum soluhility of plutonium in ? cerium is 34.5 at. pet. Invariant points in the system are: a) eutectic at 626oC, L16.5 = E Pu16.0 + y Ce65.5; b) peritectoid at613oC, e Pu13.5 -y Ce65.5- d Pu23.0. AS part of a program aimed at the determination of the phase equilibria in the Pu-Ce-Cu ternary system, preliminary investigations were made of the three binary systems. A survey of the Pu-Ce binary system by differential therma1 analysis indi- cated several areas of disagreement with the published diagram,' primarily in the shape of the liquidus surface. Consequently, a thorough investigation of the system was undertaken, and this report presents the results of the study. EXPERIMENTAL PROCEDURE Three methods of investigation were used: differential thermal analysis (DTA), metallography, and analysis with electron-microprobe X-ray analyzer (EMX). The EMX analysis was particularly useful for the determination of solvus lines. The DTA method was most useful for the determination of the liquidus curves. Metallography complemented both of these techniques. Materials. The cerium metal used for most of this work had a freezing point of 805°C. This material showed 15°C premelting, and was found metallographically to contain some unidentified in~lusions.2 The temperature of premelting is defined as the point at which the DTA curve breaks away from the base line, analogous to a curve obtained from a solid-solution alloy. Several compositions were prepared near the cerium end of the diagram with higher-purity material which had a freezing point of 800°C. etallographic analysis showed this material to be relatively free of inclusions and only 8°C premelting was observed. Major impurities were found by spectrographic

Jan 1, 1964

By W. A. Krivsky, R. Schumann

Relaxation calculations were made to find the temperature distribution in the refractory wall surrounding a tuyere pipe. One set of boundary conditions approxiwated those of a standard copper converter while a second set represented a hypothetical,thermally insulated tuyere pipe. The pvonounced cooling effect of the tuyere is related to the problem of tuyere accretions and tuyere bunching. PARTICULARLY severe service conditions are encountered in the tuyere zone of a basic copper converter during the matte blow. High-temperature gradients result from the juxtaposition of the hot charge and the tuyere pipe carrying cold air. Refractory temperatures near the tuyere mouth vary rapidly with time when the blast is turned on or off. One of the most serious problems is the formation of magnetite accretions around the tuyere mouth, which occurs very rapidly under some operating conditions. As a result, continual punching of the tuyeres is necessary to maintain a satisfactory rate of converting. Thus, if some means could be devised for keeping the tuyere pipes fully open without necessity for punching, a considerable saving should result from reduction in labor cost, maintenance of full capacity operation, and reduction in refractory costs. Recent quantitative studies of the FeO-Fe,O,-SiO, system1 have shown that the solubility of magnetite in iron-silicate slags decreases rapidly with de- creasing temperature in the range of copper converting temperatures. Data taken from the previous work are shown in Fig. 1. Thus the formation of "horns" and accretions around the tuyere mouth can result simply from the freezing out of magnetite on the cooler areas of refractory immediately adjacent to the tuyere pipes. One might expect to find a correlation between the severity of magnetite formation and the area of refractory surface which is cooled below the freezing point of the slag (corresponding to magnetite precipitation). Magnetite itself has a very high melting point (1597°C) so that the accretions are for all practical purposes infusible. The accretions might be dissolved by increasing the silica content of the slag and at the same time raising the temperature, but this approach is not feasible because it results in rapid corrosion of the basic refractory lining of the converter as a whole. In order to understand better the problems involved in tuyere design and operation, it seems essential to have at least a semiquantitative idea of the thermal conditions in the tuyere zone. Accordingly, this paper presents results of thermal calculations for an idealized copper converter tuyere. These calculations follow the so-called relaxation

Jan 1, 1960

By G. A. Bole, F. W. Davis

The purpose of this paper is not to report, to the Institute, the results so far obtained in the survey, by the Bureau of Mines, of the metallurgical requirements for open-hearth refractories, but to present an outline that we hope will serve as a basis for discussion. The systematic survey that the Bureau proposes to make has not been outlined, although considerable preliminary work has been done in the way of interviewing open-hearth superintendents in several of the larger steel plants from the Chicago district eastward. At the several conferences so many of the opinions were diametrically oppoeite, when considering the same point, that it was thought that such an opportunity as the Institute offers in the way of a clearing house for moot metallurgical topics should not be overlooked. For this reason, the paper has been prepared as a basis for a discussion which, it is believed, will be of value in outlining the program of the Bureau. D. A. LYoN, Assistant Director. The importance of securing suitable refractories for metallurgical operations is daily becoming more universally recognized; particularly in the manufacture of open-hearth steel, where the life and earning power of the furnace depends largely on the judgment and care exercised in the selection of the correct quality of refractory for each of the parts. Any innovation that would make available to the steel manufacturers refractories with longer life or better suited to their needs than those now employed, and at a cost that would permit of their use, would be of enormous value to the industry at large. It is quite probable that revolutionary changes would not be necessary. Material now used in some parts of the furnace might, by more suitable preparation, be made of much greater service; in other parts, possibly entirely different material would be necessary in order to effect much improvement. Inasmuch as different parts of the furnace structure perform different functions and are subjected to different service conditions, a refractory suitable for one part will be entirely unsuited for another. For this reason, to make a comprehensive study of the refractory requirements of the processes, we should consider the furnace as built up of a number

Jan 1, 1924

By George Mixter

MINING, in contrast to manufacturing, deals with a wasting asset. That which is taken out of the ground is gone, the property is depleted to that extent, and will eventually become exhausted of profitable ore. So the life of a mining company is dependent upon the ability of its management to develop improved methods to permit extraction at a profit of the lower-grade ores which remain, to extend by intelligent exploration the limits of its known ore bodies, and to find and acquire new properties to take the place of those that, for one reason or another, are no longer operated. Its history is a story of constant change, of the working out of properties here and the acquisition and development of properties there, to maintain the vitality of the whole. It is a story of estimating with the tools and the knowledge available the location and extent of hidden ore bodies and of devising the means of extracting

Jan 1, 1948

By A. Lubinski, C. R. Stewart, K. A. Blenkarn

Storage porosity has been considered one of the important pore geometry characteristics of heterogeneous-porosity limestones. Storage pores are only containers for fluids, in contrast to flow channel pores which both contain fluids and provide continuity for fluid flow. The concept of another geometry characteristic, "poro-striction", is presented as a second pertinent variable in describing limestone pore space. In simple terms, poro-striction is a measure of the flow resistance between storage and flow channel pores. Alternating-flow core-testing theory provides flow relationships which can be used to divide the pore space of heterogeneous-porosity media into flow channel and storage pores and to measure the "porostriction" of the latter. Experimental application of this theory to naturally occurring heterogeneous limestones shows that "porostriction" and the ratio of storage to flow channel pores can be estimated. Porostriction and porosity ratio are microscopic characteristics which should influence oil-recovery efficiencies during certain types of displacement processes. A knowledge of pore geometry should be valuable in designing or selecting the most effective oil-recovery process for heterogeneous limestones containing storage porosity. INTRODUCTION The primary and secondary recovery of oil from limestone (carbonate) reservoirs has been and will continue to be a major source of the world's supply of petroleum. Oil recovery from this type of formation is strongly influenced by the size, shape and arrangement of the pore spaces which hold the formation fluids. Therefore, it is expected that better knowledge of pore geometry would lead to design of more effective recovery processes. The concept of storage and flow channel pores has been presented as an important characteristic of limestone porosity.1 In this concept, storage pores are only containers for fluids, whereas flow channel pores are those pores which both contain and transmit the fluids. The work reported herein involves the concept of an additional pore characteristic called "porostriction". This characteristic can be visualized as the flow resistance between the storage and flow channel pores. This resistance is an important pore geometry characteristic because it determines how easily gas and oil can replenish fluids removed from the flow channel pores. Fatt and co-workers at the U. of California have studied the effect of storage porosity and a factor similar to porostriction on transient-flow response of models of porous media during a pressure build-up or drawdown test.55 These models consisted of porous sandstone cores with artificially simulated storage pores. It is the purpose of this paper to describe tests which permit the storage porosity and porostriction of actual reservoir core samples to be estimated. The tests used for this purpose involved not transient tests but, rather, an alternating-flow technique in which pressure and flow are varied according to a sine-wave relationship. This technique may offer advantages over transient methods. THE POROSTRICTION CONCEPT Before discussing alternating-flow (A.F.) tests in core samples, it is necessary to define the porostriction parameter. For this purpose attention is focused upon an elemental volume v representative of a porous medium having both flow channel pores and restricted-access storage pores. For such an elemental volume, it is considered that the storage porosity is combined to form a single pore and that the access into the storage porosity may be represented by a single capillary tube connecting the single pore to the flow channels of the elemental volume. Let the radius of the capillary tube be designated as Rc and its length as L,. When fluid flows into or out of the pore, the following equation (Poiseuille's law) relates flow rate q to pressure drop p, and the physical characteristics of the tube and the fluid of viscosity jx.

By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By J. F. Fidiam, T. F. Ford, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By T. F. Ford, J. F. Fidiam, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By Sir John Cadman

IN THE changed circumstances which now confront the world, an international open-door policy is the only way to keep pace with the world's demand for oil. You may rest assured that as far as the British Empire is concerned, American capital for the develop-ment of oil resources is welcome, and little obstruction will be found in the way to permit the use of foreign capital in the group of countries which constitute the British Empire. In the war days we worked in close cooperation and harmony, but in disbandment of the Petroleum War Service Committee, when the war ended, I feel that it left its task unfinished. In the wake of war there appeared a ghost of war-time conditions in the form of belief that Great Britain was straining to corner the petroleum resources of the world. I am certain that if the war-service committee had continued its work in the period of reconstruction the real story would be known and this sinister ghost would have long since vanished before the truth.

Jan 2, 1922