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By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953

By J. N. Chew, C. A. Connally

A correlation is presented for predicting the viscosity of gas-saturated crude oils under reservoir conditions. It is based on the dead oil viscosity and the solution GOR. The correlation was developed from a study which showed that at a fixed solution GOR, the relation between the gas-saturated oil viscosities and the correrponding dead oil viscosities is a straight line on logarithmic coordinates. Data from 457 crude oil samples from the major producing areas of the U. S., Canada and South America were used. The best straight lines through the data were fitted by the method of least squares with a digital computer. The correlation is presented in the form of an equation and also in a convenient gra-phical form. INTRODUCTION The viscosity of gas-saturated crude oils under reservoir conditions is an important physical property used in reservoir engineering calculations. Many difficulties are inherent in the sampling of gas-saturated oils and in the laboratory measurement of their viscosities. Therefore, it is frequently neither possible nor convenient to obtain measured values, so the viscosity must be estimated from other, more readily available data. This paper presents a correlation for predicting the viscosity of gas-saturated crude oils. The correlation is based on the amount of gas in solution and the viscosity of the dead oil at the temperature of interest. A previous correlation of these variables was presented by Beal. In comparison, the correlation presented here extends to a higher GOR and to a lower dead oil viscosity. Over the range of variables covered by both, this correlation is based on approximately 11 times as many oil samples. DEVELOPMENT OF CORRELATION A study was made of the variables or parameters which could be used to relate the viscosity of a gas-saturated oil to its dead oil viscosity. Preference was given to those variables which are easily and commonly measured in the field or in the laboratory. It was found that either the differential liquid formation volume factor or the solution GOR of the gas-saturated oil could be used as a correlating parameter. The solution GOR was se- lected for the correlation because of its simplicity and availability. In an attempt to refine the correlation by introducing a second parameter, the following additional variables were tested: differential liquid formation volume factor at the reservoir bubble point, the formation volume factor at the saturation pressure for the GOR of interest, reservoir temperature, viscosity of C+ fraction at 100°F and atmospheric pressure, weighted average gravity of gas in solution, oil gravity, reservoir bubble point pressure, saturation pressure at the selected GOR and reservoir temperature, and gas mol fraction. None of these improved the correlation to any significant extent. It was found that at any fixed solution GOR, the relation between the gas-saturated oil viscosities and the corresponding dead oil viscosities is a straight line on logarithmic coordinates, for the range of variables investigated. This straight-line relationship was used for the correlation. Viscosity data on a total of 457 crude oil samples were used. The data were obtained with rolling ball-type viscometers. The samples came from all of the important producing areas of the U. S., as well as from Canada and South America. Their geographical distribution is shown in Table 1. The ranges of properties represented by these samples are as follows: For each crude oil sample the viscosity of the liquid phase from each step of a differential liberation was plotted against its solution GOR on semi-logarithmic paper. A smooth curve was drawn through the points and values of viscosity in centipoises were read from

By L. L. Swift

AT the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows in some types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing metal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cient of friction. Under most operating conditions the friction depends on the unit pressure of the bearing, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.1 The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measure-ment of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual constituents was developed to fill this need.

Jan 1, 1938

By Claus G. Goetzel

Pressing of powdered metal parts is best done in the direction of the shortest extension of the piece, to avoid too great a loss of pressing force through internal iriction. As long as curved surfaces, re-cessej, or offsets occur only parallel to this shortest axis of pressure, no special difficulties arise: the cross sections, perpendicular to the pressure, do not vary, nor does the shape of the parts change during compression except for a gradually reduced thickness (Fig. IA). The problem becomes more dificult, however, when the curved surfaces or recesses are perpendicular to the shortest axis of the part (Fig. IB) Two processes for molding uniformly dense parts with complicated shapes from powdered metals are described in detail in this paper. Both can be employed successfully by those trained in the art. The first refers to curved parts; the second is especially adapted to parts having one or more recesses or steps. Both methods, as set forth here, are applied under the condition that presents the more difficult problem. For clarity, before description of the two practical methods, the variable factors in molding powdered metal parts will be reviewed, then an idealized procedure will be considered briefly. Variable Factors in Molding Powdered Metal Parts Compression Ratio Compression ratio is defined as the proportion of the final relative density of the compact to the apparent density of the powder. For iron powder of an apparent density of 3.0, for example, a compression ratio of 2 1/2:1 would be required to produce a compressed compact of 7.5 density; whereas for another iron powder having an apparent density of only 1.5, a compression ratio of 5:1 would be required to produce the same density. The lower the powder's apparent density, the greater must be the compression ratio for pressing compacts of high density.

Jan 1, 1946

By Claus G. Goetzel

Pressing of powdered metal parts is best done in the direction of the shortest extension of the piece, to avoid too great a loss of pressing force through internal iriction. As long as curved surfaces, re-cessej, or offsets occur only parallel to this shortest axis of pressure, no special difficulties arise: the cross sections, perpendicular to the pressure, do not vary, nor does the shape of the parts change during compression except for a gradually reduced thickness (Fig. IA). The problem becomes more dificult, however, when the curved surfaces or recesses are perpendicular to the shortest axis of the part (Fig. IB) Two processes for molding uniformly dense parts with complicated shapes from powdered metals are described in detail in this paper. Both can be employed successfully by those trained in the art. The first refers to curved parts; the second is especially adapted to parts having one or more recesses or steps. Both methods, as set forth here, are applied under the condition that presents the more difficult problem. For clarity, before description of the two practical methods, the variable factors in molding powdered metal parts will be reviewed, then an idealized procedure will be considered briefly. Variable Factors in Molding Powdered Metal Parts Compression Ratio Compression ratio is defined as the proportion of the final relative density of the compact to the apparent density of the powder. For iron powder of an apparent density of 3.0, for example, a compression ratio of 2 1/2:1 would be required to produce a compressed compact of 7.5 density; whereas for another iron powder having an apparent density of only 1.5, a compression ratio of 5:1 would be required to produce the same density. The lower the powder's apparent density, the greater must be the compression ratio for pressing compacts of high density.

Jan 1, 1946

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,' it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert's apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By J. P. Boisseau, C. N. J. Wagner, E. N. Aqua

An analysis ulas made of powder-paltern peaks from cold-rolled polycrystalline copper and from copper powders, compacted into briquets (1 in. diameter) with pressures up to about 106 psi. Powder-pattern peaks from both contact faces were measured with a diffractometer and CuKa radiation. Laltice-parameter measurements indicate the presence of residual stresses in the bulk specimen of the order of a - -10 kg per sq mm after 93 pct reduction in thickness, and give some evidence for the occurrence of deformation stacking faults (probability a - 0.003) in both bulk and powder samples. Fourier analyses of the line profiles were carried out on the (111) - (222) and (200) - (400) Pairs of reflections. The particle sizes decrease rapidly with increasing deformation and reach asymptotic values of De (111) = 550A and D, (200) = 350A at about 25 pct reduction in thickness or 80,000 psi pressure for compaction. The anisotropy of the particle sizes indicates the presence of microtwins and stacking faults on (111) planes. The rms strains increase also with deformation and reach limiting values of 2 x 10-3 in the [100] direction and 1 x 10-3 in the [Ill] direction at a distance L = 100A normal to the reflecting planes. THE diffraction of X-rays in cold-worked, polycrystalline, fcc metals and alloys yields Debye-Scherrer patterns in which the individual (hkl) lines may show a broadening, a shift, and an asymmetric shape.' These effects can be explained by the fragmentation of the small, coherently diffracting domains, the presence of residual elastic strains in the lattice, and the formation of stacking faults. X-ray studies of stacking faults in fcc metals and alloys have been methodically performed during the last few years, but so far most of the investigators dealt with cold-worked powder specimens obtained by filing.2-8,10-19 In such specimens, the crystals are randomly oriented and the average elastic strains are assumed to be zero, so that the observed peak shifts are due to stacking faults only. The agreement between X-ray diffraction theory1,20 and experiment is generally good. On the contrary, cold-worked, polycrystalline bulk specimens (after wire drawing, rolling, plastic deformation by tension or compression, etc.) contain residual elastic strains, which may not average to zero in the surface of the specimen and show very strong preferred orientation of certain lattice planes (texture) parallel to the specimen surface. Nonzero elastic strains also produce peak shifts, the magnitudes of which depend upon the crystallographic orientation of the reflecting lattice planes in elastically anisotropic materials as well as on the type of plastic deformation and which have to be taken into account when measuring stacking-fault probabilities in deformed bulk specimens.21-23 The purpose of the present investigations was to perform a detailed X-ray analysis on a bulk specimen of a fcc metal deformed by rolling at room temperature and on powder of the same material deformed by compaction, and to compare these results with those previously obtained on cold-worked filings.18 Pure copper was chosen for this study since it is known to produce only a small quantity of stacking faults by filing at room temperature.3,16,17,19 The residual elastic strain in the surface of the bulk copper should be the predominant factor determining

Jan 1, 1965

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By Frank Harris

THE strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chemical and physical considerations, the high conductivity required for copper wire in the electrical industry generally precludes the possibility of obtaining tensile strength through the use of alloys. Consequently, this strength is largely a matter of the physical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., are matters of prime importance. The experiments described here have been carried out during the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigation of some of the questions mentioned above, with the object of studying the physical structure of hard drawn copper, wire and the influence of certain factors on that structure. The work has been of an exploratory nature, rather than comprehensive, but it was thought that the results might prove of sufficient general interest to warrant their publication. The bulk of the hard drawn copper wire used in places where strength is an important factor is manufactured to strict specification, based usually in the United States on that of the American Society for Testing Materials (B-1-23). This specification calls for almost as high a value of tensile strength; consistent with elongation, as it is possible practically to obtain, and only physically perfect material can be relied on to meet such a specification. Obvious defects, such as laminations produced through fins in the original rods or brittleness due to overdrawing, are usually recognized and need only passing reference. Laminations can be detected by twisting and untwisting the wire several times; they will show up on the surface in the form of fins. Fig. 1 shows a very bad example of this defect. The wire may be perfectly smooth before twisting but when such laminations are present they will readily show up under this treatment. This trouble is caused by similar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which the wire in Fig.1 was drawn.

Jan 1, 1928

By J. G. Eenink, R. A. Cunningham

One phase has been completed of a laboratory invesrigation of formations with relatively high permeability under conditions of overburden, formation and mud coltrmn pressures. The following statements are based on these tests within the limitations described. Drilling rate decreased when mud column pressure was greater than formation pressure. The decrease was primarily due to a layer of cuttings and mud particles held to the hole bottom by the difference in pressure. Much of the force of the bit was wasted in this layer and was unavailable for penetrating virgin formation. Adequate jet velocities helped clean the filter cake and chips away and resulted in increased drilling rate — the higher the jet velocity the faster the drilling rate. Drilling rate increased slightly when formation pres sure was greater than mud column pressure. The i11(reuse resulted from cleaning the hole bottom as formarion fluid flowed into the borehole. Overburden pressure had practically no effect on drilling rate. INTRODUCTION Some formations are difficult to drill in a wellbore hole but are easily drilled under atmospheric conditions in the laboratory. The reasons for this apparent difference in drillability are not fully understood. An increase in formation compressive strength causes a reduction in drilling rate. It has been shown by Griggs1, Handin2 and others3-1 that formation strength increases under conditions of high hydrostatic stress. Based on these results, a decrease in drilling rate would be expected with increased drilling fluid pressure in formations of low permeability having low formation fluid pressure. Such a decrease has been shown by Murray. et a1 and Eckel" This effect holds even when using nitrogcn under high pressure as the drilling fluid (unrc-ported tests from the Hughes laboratory). Poor bottom-hole cleaning may account for decreased drilling rates. Even though it may not be easily explained, evidence of poor cleaning can easily bc seen. One evidence is the increased drilling rate that accompanies decreased balling obtained with addition of oil in some muds used to drill shales.4,7,3 Many variables can affect drilling rates. These may include mud composition and properties, formation properties, bit types and operating conditions, formation fluid, mud column and overburden pressures. These must be studied a few at a time under carefully controlled conditions which simulate actual conditions as closely as possible. The purpose of this work was to investigate effect of overburden, formation and mud column pressures on drilling rates in permeable formations. These tests were suggested by conditions shown in Fig. I. Represented is a borehole drilled into a formation with relatively high permeability. In the vicinity of the hole bottom there exists a mud column pressure, P a formation fluid pressure, P and an overburden pressure, The mud has low water-loss properties and sufficient weight to more than overbalance the formation pressure. Laboratory investigation included a range with formation pressure greater than mud column pressure. NOMENCLATURE Pm mud column pressure = pressure of drilling fluid or mud at hole bottom Pf, formation pressure = pressure of fluid in intersticies of formation

By John M. Dealy, Robert D. Pehlke

Values for interaction parameters in nonferrous systems, as calculated from published data, are tabulated and discussed. The influence of temperature on the parameter is derived and compared with the results of the literature study. Wagner's relationship between the interaction parameter and the self interaction coefficients is compared with the tabulated data. A problem which has been of considerable interest in the field of metallurgy is the prediction of the effect of one alloying element present in dilute concentration on the thermodynamic properties of another dilute alloying element. Ultimately, the prediction may be accomplished entirely from statistical mechanical considerations. At the present, however, the problem remains unsolved since liquid solution models which are simple enough for analytical treatment are inadequate for such purposes. Thus, we desire some means of organizing the information on dilute systems which will serve as a guide for further study on interactions in dilute alloys, and also provide a basis for the utilization of thermodynamic data in the engineering design of alloys.

Jan 1, 1963

By Laurence Delisle

The aim of this paper is the description of a technique to be applied to the study of sections of metal powder particles, less than 20 microns in diam. with the electron microscope, by the replica method, using for replica a material such as formvar or parlodion. This work originated with the study of particles of tungsten powders. Such particles were too small to be examined in sufficient detail with the light microscope. On the other hand, examination with the electron microscope of the powders dispersed in the supporting film was not found satisfactory because: 1. It did not permit differentiating between single particles and aggregates. 2. It did not show the true outlines of the particles but only the projection of a whole surface. 3. No details appeared. For that reason it was attempted to make replicas of sections of the particles imbedded in a mounting material suitable for polishing and etching. The method proved satisfactory for the examination of tungsten powder and was then extended to car-bonyl nickel and carbonyl iron powders. Procedure Several mounting materials commonly used in ordinary metallography were investigated. The problem consisted in finding a mounting material

Jan 1, 1950

By H. H. Uhlig

Soon after general use of stainless steels began, it was observed in practice that certain combinations of factors tended to induce corrosion by pitting. For most applications this was a serious drawback, not so much because the structural properties of the metal were impaired but because of the rapidity with which heavy sections of the alloys were penetrated by small elongated pits. These pits seemed to initiate readily in oxidizing metal salt solutions like ferric chloride and in chloride solu-tions like sea water. It was observed that in sea water pitting was more frequent in stagnant or polluted waters than in highly aerated, moving waters. The steels in these chloride solutions were observed to be sensi-tive to long contact with material such as sand grains or attached bar-nacles. At points of attachment or contact it was not uncommon to discover initiation of corrosion. Pits once begun at contact faces were observed to grow rapidly, usually elongating phenomenally in the direc-tion of gravity until the metal was perforated. Hydrochloric acid and other nonoxidizing acids, on the other hand, were observed to corrode stainless steels generally; the weight losses often were higher, but the penetration less than for the pitting type of corrosion. The causes of pitting, a type of corrosion recognized as character-istic not only of stainless steels but of many additional metals and alloys, are important in corrosion studies. A possible explanation bears prac-tical significance, for once it is known why pits begin where they do and continue to grow after initiation, intelligent direction can be given to diminishing corrosion. This can be done either by some alteration in the composition and treatment of the alloy or by some alteration in the environment. It appears foremost in importance to discover the nature of pit foci, for if initiation of pits can be discouraged their growth will be no longer a factor to be considered. In a multi-component alloy containing many impurities normal to production of such an alloy, each of which may play a part in pitting, and whose corrosion resistance is sensitive to heat-

Jan 1, 1940

By John A. Church

When, in 1879,I examined the mines of the Tombstone Mill and Mining Company, at Tombstone, Arizona, I found a bed of tailings containing 12,000 tons, which had a value of 9 to 12 ounces of silver per ton and some gold. The ore had been amalgamated in pans, in which each charge had been ground for four hours, having been pre viously stamped through rough-punched screens, which gave a pro duct varying from 1-100th to 1-20th of an inch, according to the state of wear of the screen. It was certain that a large proportion of the tailings must be in fine slimes, and the question of recovering their value was difficult. Even now the concentration of slimes is . an unwelcome task, and at that day very little was known about it. Nevertheless, after considering the results of a test by repanning the tailings, I advised the company to concentrate and smelt, although they had to face the difficulty of making a smelting-product from slimes containing only 3 per cent. of lead. Limestone was abundant enough, but no iron suitable for flux was to be had for hundreds of miles. One of the company's claims con tained an argeutiferous manganese-ore, which gave but poor results by amalgamation. This was one reason for recommending smelt ing ; for if manganese would play the part of a precipitant, as iron does, the company could smelt by combining two of its silver ores, without other flux than the small amount of lime that might be needed. At that time no smelter had ventured to trust manga nese as a precipitant, though large quantities of this ore containing silver were bought and used by custom-smelters, who looked upon the manganese solely as a basic flux for silica. I believe that no other furnace has been obliged to trust this metal, and that the man ganese practice of Tombstone remains unique among the records of smelting lead-ores in the shaft-furnace. The bright side of the problem was given by the fact that the mines were shallow and that the enterprise would at least begin with oxidized ores. The tailings contained about 85 per cent. of silica,

Jan 1, 1895

By H. C. George

CAREFUL- sampling and good judgment as to probable recoveries are important factors in estimates of ore reserves, based on prospecting drilling results, but other factors are equally as important and may be more misleading and perhaps disastrous if not properly interpreted. Some of these are: 1. The case where no, ore is shown in the "sludgings," when, as a matter of fact, the drill has passed through a thick sheet of ore which has been broken up and washed away into open crevices. In numerous cases, later mining operations have shown that this has happened. This condition may be discovered by shooting the drill .hole at the point where the open crevices occur, but shooting should not be done until after the drill hole is completed, because the resulting shattered formation may salt the drill hole at lower levels. 2. The case where rich cuttings are shown for a thickness of 20 or 30 ft., when ore was encountered in only the first sludging. Owing to soft or loose formation, the ore from the first sludging has salted the lower sludgings. The presence of large pieces of ore and a similar ratio between zinc and iron assays in the lower sludgings frequently indicate this condition. In the lower sludgings, the presence of oxidized ore in unaltered limestone sometimes shows this condition. 3. The case where the drill hole shows a considerable thickness of ore; but owing to the presence of a vertical sheet of ore, perhaps not more than 1 in. thick, at the place where the drill hole is located, the good assays resulting might be misleading. If this condition is suspected, the drilling of several more holes within a distance of 10 or 15, ft. will usually show it.

Jan 1, 1921

By Charles G. Maier

It has long been supposed that when crystalline materials are comminuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1.t The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chemical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the corrected heat of solution was less for fine material than for coarse. Continuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. Similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by Rosenhain and Stott4 and by Taylor and Quinney9 The results obtained by the different investigators were not satisfactorily consistent, but the experiments of Taylor and Quinney constitute by far the best figures obtained to date. The previous paper1 presented evidence to show that if energy is stored in the surfaces of crystals the densities of fine crystals should differ

Jan 1, 1936

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto' proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer's analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956

By V. C. Allison

The explosibility of a dust is favored by its fineness and content of volatile combustible matter; its explosibility is decreased by its moisture and ash content. The explosibility of a dust can be reduced by admixture of either inert dust or water. The major effect of both the inert dust and water lies in their heat capacity; they absorb the heat of the explosion flame until the temperature of this flame drops below the ignition temperature of the explosive heat. The amount of inert dust necessary to make an explosive dust non-explosive can be calculated from its proximate analysis. FOREWORD LARGE-SCALE testing of the explosibility of coal dust as conducted by the Bureau of Mines in its Experimental Mine involves a large initial investment, and a high charge for maintenance and conduct of the test; in addition the work is necessarily slow because of the time required for the preparation of the tests and the cleaning and repairing of the mine after each test. These tests have been made along practical mining lines that admit of a range of mixtures of dust varying from 5 to 10 per cent. and with gas as low as 0.5 per cent. increments. Because of the time and expense involved, efforts have been made to devise a type of gallery for laboratory use in which the results obtained in the Experimental Mine may be correlated as an aid in a study of dusts, the explosibility of which might be approximately determined quickly and at a minimum of expense. The explosibility of coal dust has been studied by a number of European investors, using small laboratory devices; among these may be mentioned the experiments con¬ducted by Galloway, Vital, Hall and Clark, Abel, Mallard and Chatelier, Thorpe, Bedson and Widdas, Engler, Holwartz and Meyer, and Taffanel, results of whose experiments have been reviewed by the Bureau of Mines., The Bureau has conducted many tests with the Frazer-Clement2 apparatus, which gives the pressures set up when the dust cloud within is, ignited with a platinum coil or tube, heated to different temperatures, but for these tests the sample must be especially prepared as to size (200 mesh) and must be dry. An attempt has been made to design an apparatus that may be used for checking and correlating the experimental tests. The first design was a wooden gallery, 8 by

Jan 7, 1925

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.' These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf's associated with permeable formations are now understood to consist of liquid-junction emf's and membrane emf's.',' As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf's just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.