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By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu's coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.' Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute's influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger's argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.' Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute's influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute's influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968

By L. W. Holm

Laboratory flooding experiments on linear flow systerns indicated that high oil displacement, approaching that obtained from completely miscible solvents, can be attained by injecting a small slug of carbon dioxide into a reservoir and driving it with plain or carbonated water. Data are presented in this paper which show the results of laboratory work designed to evaluate this oil recovery process, particularly at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi. Under these conditions CO2 exists as a dense single-phase fluid. It was found that a bank, rich in light hydrocarbons, was formed at the leading edge of the CO? slug during floods on long cores. Formation of this bank is probably due to a selective extraction by the C02 and, it is believed, partially accounts for the attractively high oil recoveries. In crddition to the efficient displacernerlt of oil from the pores of the rock by this process, the favorable rnobility ratio related to a C0 2-water flood also contributes to high oil recovery. A further advantage of this process is noted on limestone and dolomite rock, in that the CO1 reacts with the porous medium increasing its permeability. Flooding experiments were conducted on sandstone and vugular dolomite models. The results of this experimental work show the effect on oil recovery of type of porous medium, pore geometry, flooding length, and flooding pressure. The porosity of the cores and rilodels varied from 16 to 21 per cent and their pern~eabilities ranged from 100 to 200 md. A reconstituted West Texas reservoir oil, a West Texas stock tank oil, an East Texas stock tank oil and Soltrol were used to represent reservoir oils in this study. Oil recoveries ranging from 60 to 80 per cent of the original oil in place in these cores were obtained by CO2,-carbonated water floods at pressures between 900 and 1,800 psi, compared with conventional solution gas drive and water-flood recoveries of 30 to 45 per cent on the same cores. Oil recoveries greater than 80 per cent resulted frorn f1oods at pressures above about 1.800 psi. There high recoveries were noted from both the sandstone and the irregular Porosity carbonate cores. In all floods, additional oil was recovered by a solutiorr gas drive resulting from blowdown following the flood. Oil recoveries of 6 to 15 per cent of the original oil in place were obtained during this blowdown period. This additional recovery was found to be a function of oil remaining after the flood, decreasing with decreasing oil saturation. It was also noted that highest oil recoveries by blowdown were obtained when carborlated water rather than plain water followed the CO, slug. INTRODUCTION Miscible phase or solvent flooding processes, which are designed to increase oil recovery -from petroleum reservoirs, involve the injection of small quantities of a petroleum solvent into the reservoir, followed by an inexpensive scavenging fluid which is miscible with the solvent. Essentially complete displacement of oil from the pores of reservoir rock has been obtained by this technique. CO,, although not completely miscible with most reservoir oils at moderate pressures, is highly soluble in these oils at pressures above about 700 psi; there is appreciable swelling and reduction in the viscosity of oil when CO, is dissolved in it. Therefore, CO, could be expected to perform similarly to other oil solvents as a displacing agent. CO, is also highly soluble in water at elevated pressures, so water should be a satisfactory material to drive a slug of CO, through an oil-bearing reservoir. A favorable mobility ratio would be obtained through the reduction in viscosity of the oil and the use of water as a final displacing agent. A number of investigations of the use of CO, to improve oil recovery have been reported in the literature.2,3,4,5,6 These studies, however, have been conducted on uniform porosity sandstone at relatively low temperatures and pressures. The behavior of CO1 as a flooding agent at temperatures above its critical temperature could not be predicted adequately from these studies, particularly for the case of non-homogeneous rock. The purpose of this work was to evaluate the oil recovery efficiency of a process involving the injection of a CO2 slug followed by carbonated water, at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi, and to compare this process with conventional water flooding. The investigations were primarily designed to provide information on the efficiency of the process in irregular porosity carbonate rock. The effects of flooding path length, the presence of free gas, the type of oil to be recovered, and the amount of solvent required were also determined. The essential results of static phase behavior studies and experimen-

By M. L. Rudee, R. A. Huggins

Samples of iron containing nitrogen or carbon have been given treatments similar to those used in cold-work peak (CWP) measurements and examined by transmission electron microscopy. It was observed that the unusual and nonreproducible behavior of the carbon CWP can be explained by a strong tendency for carbon to form grain boundary precipitates at temperatures below those used for CWP measurements. These precipitates dissolved at the temperatures used in the CWP measurements. There was no evidence for nitrogen precipitation at grain boundaries. There was no indication of precipitation along dislocations in either carburized or nitrided samples given treatments similar to those of CWP measurements. Although it is possible that subelectron-microscopic clustering had occurred, this observation supports the theories of the CWP that are based on continuous atmospheres rather than on individual precipitates. In an earlier paper,' the present authors developed a new distribution function to predict the occupation of sites for interstitial impurity atoms around a dislocation. When this distribution was applied to the case of carbon and nitrogen in iron, it predicted that, if the temperature dependence of the concentration of solute atoms in the matrix was controlled by the presence of equilibrium carbide or nitride precipitates, the tendency for nitrogen to segregate to dislocations would be greater than that for carbon even though their binding energies to dislocations are identical. The cold-work internal-friction peak (CWP) is considered by most authors to be produced by the interaction of interstitial impurities with dislocations. Many investigators have studied the CWP in iron containing carbon and nitrogen and have observed a significant difference between its behavior in the two cases. In this paper a series of experiments will be reported that were initiated to determine whether the application of the new distribution function would explain the observed differences between the carbon and nitrogen CWP. Although it was found that the distribution function, pev se, did not explain the differences, the differences became clear, and some insight into the mechanism of the CWP was realized. Before reporting the present experiments, the literature pertaining to the differences between the carbon and nitrogen CWP in iron and the various mechanisms proposed for the CWP will be reviewed. LITERATURE REVIEW Snoek2 first observed the CWP in iron specimens containing nitrogen, but also reported a weak and unreliable peak in carburized samples. Later, Ke3 established that the CWP height was proportional to the degree of deformation. The presence of nitrogen alone would produce a peak of the same size as found in a sample containing both nitrogen and carbon, and KG concluded that the CWP was caused by nitrogen. In a discussion of G's paper it was reported that Dijkstra had investigated the CWP in samples that contained only carbon. He found it to be much smaller than the nitrogen peak and "unstable". KG et al.4 charged specimens of iron with both carbon and nitrogen. They observed that the carbon CWP was much smaller than that observed in nitrided samples, but that aging at 300°C caused the carbon peak to increase. A similar treatment produced no change in a nitrogen peak. Annealing at higher temperatures caused the height of the CWP in both the nitrogen and carbon samples to decrease. This behavior was also observed by Kamber et al. 5 who found that the activation energy for the annealing of the CWP was identical with the activation energy for the self-diffusion of iron. They concluded that the annihilation of dislocations by climb caused the reduction in the CWP height. Kamber et al. studied the "unstable" carbon peak in detail. They measured both the Snoek and CWP during various aging treatments. In carburized samples, aging at 100°C caused the Snoek peak to disappear, although the CWP peak remained small. However, a subsequent treatment for 5 hr at 240°C caused the CWP to reach a maximum. They proposed that an additional location for the carbon, other than whatever site produced the CWP, is present. In nitrided samples the CWP was completely developed as soon as a measurement was made; additional sites are not present. No explanation of either the additional site or the difference in the behavior of carbon and nitrogen was offered. petarra5 performed a systematic study of the effect of composition on the CWP. Using three kinds of "pure" iron, he showed that there was a residual CWP when the carbon and nitrogen concentrations had been reduced to less than that detectable by Snoek-peak measurements. He observed the same general annealing behavior and composition dependence as previous investigators, with the following exceptions. On first measuring the carbon CWP, it was found to be identical with the residual peak, and essentially independent of the carbon content. If the CWP was measured a second time in the same sample, it increased in size, but was still only about one-fourth the size of a CWP in a sample of the same iron nitrided to the same composition. On the other hand, a series of annealing experiments showed that the nitrogen CWP was not al-

Jan 1, 1967

By J. A. Bailey, J. H. Tundermann

The dihedral angles of the solid-liquid interfaces were measured at various temperatures above the solidus and the interfacial energies calculated when small additions of copper, indium, lithium, magnesium, antimony, and silicon were made to an aluminum alloy containing 3 pct Sn. When the results were compared with those of the Al-Sn alloy some differences were found which could be interpreted in terms of the ability of the added element to enter into solution or form intermetallic compounds with the aluminum and tin. It was shown that in some cases considerable changes in the shape of intergvanular liquid films can be brought about by comparatively small compositional changes in the alloy. DURING the melting or solidification of an alloy a temperature range is usually found where the presence of a liquid phase may be detected at the grain boundaries of a solid. It is believed that the presence of this liquid phase is responsible for hot tearing in castings and welds and hot shortness in the working of some alloys at elevated temperatures. Rosenberg, Flemings, and Taylor1 in a study of the solidification of aluminum castings have indicated the importance of intergranular liquid films and shown that their shape and distribution at the end of solidification effect the hot tearing characteristics of the material. The shape of such intergranular liquid films are determined largely by the ratio between the solid-liquid interfacial energy (yLS) and the grain boundary energy (ySS). A measure of this ratio (yLS/ySS , relative interfacial energy) is the dihedral angle 8. The dihedral angle 0 is related to the relative interfacial energy by the following expression: Rogerson and Borland 2 have also suggested that the shape of the intergranular liquid is an important factor in determining the susceptibility of a material to hot shortness. They showed that on a comparative basis materials having the lowest dihedral angles at a given temperature gave the greatest severity of cracking. They stated that liquid in the form of globules should be less harmful than liquid in the form of extensive films as more intergranular cohesion should be possible. Rogerson and Borlland 2 also showed that the susceptibility of an A1-Sn alloy to hot cracking can be reduced by small additions of cad- mium. It was found that the cadmium gave an increase in the dihedral angle at all temperatures. Ikeuye and smith3 investigated changes in the dihedral angle and relative interfacial energy with temperature for a number of ternary alloys formed when small additions of bismuth, cadmium, copper, lead, and zinc were made to an A1-Sn alloy. They found that in most instances changes in the dihedral angle were caused by compositional changes in the liquid phase; as the composition of the liquid approached that of the solid the dihedral angle decreased. They noted that the addition of a third element which was soluble in both the liquid and solid phases at a given temperature may decrease the dihedral angle (e.g., the addition of copper or zinc) but otherwise the ternary alloys formed exhibited dihedral angles between those of the A1-Sn binary alloy and those of the binary alloy of aluminum with the added element. Dwarakadasa and Krishnan4 investigated the changes in dihedral angle and relative interfacial energy with temperature when small additions of magnesium, iron, silicon, manganese, sulfur, cobalt, and silver were made to a copper alloy containing 3 pct Bi. They found that in all cases the added elements gave an increase in the dihedral angle and relative interfacial energy when compared with the values obtained for the simple binary alloy at the same temperature. It was noted that an increase in temperature gave a decrease in dihedral angle and relative interfacial energy in each of the ternary alloys studied. Similar results have been obtained by Ramachandran and Krishnan5 for the addition of small quantities of lead. This paper describes the application of dihedral angle measurement to the determination of the shapes of liquid phases at various temperatures above the solidus when small additions of copper, indium, magnesium, lithium, antimony, and silicon are made to an aluminum alloy containing nominally 3 pct Sn. An attempt is made to correlate the measurements with the relative solubility of the added elements in tin and aluminum. The work was undertaken to provide more data concerning the effects of temperature and composition on the shape of liquid films above the solidus. EXPERIMENTAL PROCEDURE In the present work ternary aluminum alloys containing nominally 3 pct Sn and small additions of high-purity copper, indium, lithium, magnesium, antimony, and silicon were made. The alloys were melted in a graphite crucible under an inert atmosphere of argon and cast into ingots 6 in. long by 0.5 in. diam. The ingots were then cut into rods 1.5 in. long, given a 50 pct cold reduction, and machined into test pieces 0.5 in. long by 0.5 in, diam for heat treatment. The alloy samples were annealed at the various test temperatures between the liquidus and solidus for approxi-

Jan 1, 1967

By W. F. Chiao

Ultrasonic attenuation, a, measurements in the frequency range of 5 to 55 mc per sec have been studied to determine their quantitative relationship with the following three variables of mixed microstructures in steels: 1) the volume percent, XF, of polygonal fer-rite in mixed structures of martensite and polygonal ferrite in Fe-Mo-B alloys: 2) volume percent, XA, of retained austenite plus martensite aggregates in high-carbon steel; and 3) substructural differences between 100 pct bainitic ferrite structures formed at various temperatures. The quantitative relationship obtained in the first two conditions by plotting a us the known structural parameters can be expressed, respectively, as: where al, a 2 and C1, Cz are constants. In the third condition the nature of the attenuation depends on the state of dislocations generated at the transformation temperatures and also on the alloy composition. From these measured results, the mechanism of ultrasonic attenuation caused by these mixed microstructures can also be studied. MUCH interest has recently been shown in the application of ultrasonic attenuation and wave velocity measurements to the study of the microstructural characteristics of steels. The general aims of most of the investigations in this field can be grouped into two categories: one is to study the mechanisms of ultrasonic losses caused by the characteristic phases in the microstructure of steel,''' and the other is to develop nondestructive test methods and applications for quality control.~' 4 Apparently no work has been done on the evaluation of ultrasonic attenuation meas -urements as a means of quantitative determination of a given phase in the microstructure of a steel. It is well-established that the decomposition of austenite results in four main microstructural constituents—polygonal ferrite, pearlite, bainite, and martensite—and that each phase has different mechanical properties. Thus, when a steel consists of mixed microstructures, the mechanical properties can often be related to a quantitative measure of the volume percent of each phase present. This study relates ultrasonic attenuation measurements to: 1) the volume percent of polygonal ferrite in mixtures of martensite and polygonal ferrite in Fe-Mo-B alloys; 2) the substructural differences between 100 pct bainitic ferrite structures formed at various temperatures; and 3) the vol- ume percent of austenite in austenite plus martensite aggregates in a high-carbon steel. The choice of the specimen materials was based on the laboratory stocks which were suitable to produce the required mixed microstructures for this study. EXPERIMENTAL PROCEDURES Materials and Heat Treatment. Polygonal Ferrite Plus Martensite Structures. This mixture of phases was produced in a vacuum-melted Fe-Mo-B alloy. The alloy was hammer-forged at 1900" ~ to a -f-in.-sq bar. By isothermally heat treating the alloy at 1300° F for various times and then water quenching, variations in the amount of polygonal (or proeutectoid) ferrite can be controlled in a microstructure in which the balance of the material is martensite. In the present work, four different times of isothermal transformation were adopted; after heat treatment, the four specimens were machined for ultrasonic measurements. The compositions, heat treatments, and dimensions of the four specimens are listed in Table I. 100 pct Bainite Structures Formed at Different Temperatures. It has been well-established by Irvine et al.= that the presence of molybdenum and boron in ferrous alloys can retard the formation of polygonal proeutectoid ferrite and expose the bainitic transformation bay, so that a more acicular or bainitic ferrite can be obtained over a wide range of cooling rates. Their investigation6 also showed that the mechanical properties of fully bainitic steels are usually closely dependent on the substructural characteristics of the steels. For studying the substructural characteristics in completely bainitic structures, six Fe-Ni-Mo alloys, of which five were free from carbon addition and one with 0.055 pct C addition, were selected so that a wide range of hardness values for 100 pct bainitic ferrite structures could be produced by normalizing at 1900" F followed by air cooling. The different bainitic transformation temperatures were recorded during air cooling. All of the alloys were vacuum-melted and then forged at 1900" F to square bars. Data on the six specimens of these structure series are summarized in Table 11. Austenite Plus Martensite Structures. The high-carbon steel used to study austenite plus martensite structures was vacuum-melted and then forged into Q-in.-sq bar. The series of mixed structures of austenite plus martensite was produced by quenching the specimens from the austenitizing temperature to room temperature and then refrigerating them at various temperatures within the range of martensite transformation to produce different amounts of retained austenite. Data on the four specimens of this series are listed in Table 111. Quantitative Analysis of the Microstructures. The microstructures containing martensite plus polygonal ferrite were analyzed by the point-counting technique.

Jan 1, 1969

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts' method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s'- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts' apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts' method was used for this study and followed the procedures outlined previously.l' The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts' law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts' law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van't Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,' and Humbert and 1liott.l' The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i'- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967

By J. R. Cahoon, H. W. Paxton

The possibility of using unidirectionally solidified, two-phase alloys as an approximation to fiber composite materials is investigated. The short-term me.chanical properties and failure modes of unidirectionully solidified A1 (rich)-Cu alloys containing ap -Proximately 0, 17.5, and 27.7 vol pct of 0 phase 'fibers" are determined at temperatures from 25" to 500" and compared with those obtained for conventionul SAP alloys. In a previous publication,' hereafter referred to as I, the possibility of understanding some of the room-temperature mechanical properties of unidirectionally solidified castings was explored. For Al(rich)-Cu and Al(rich)-Mg two-phase alloys over a substantial range of compositions, the yield and ultimate strengths and common ductility measures were very adequately predicted from the principles of fiber strengthening4 and the analysis of ductility outlined by Gurland and Plateau." The results obtained in I suggest the possibility of using unidirectionally solidified, two-phase alloys to simulate fiber composite materials where the inter-dendritic second phase or constituent acts as the reinforcing material. Recent attempts concerning the fabrication of fiber conlposites have concentrated on producing composites with a good bond between fiber and matrix and with very long fibers so that their maximum contribution to the strength of the composite may be realized. However, these objectives are difficult to attain in practice and present fabrication processes are either extremely laborious or costly.13 The slow, unidirectional solidification of eutectics has received considerable attention as a method for producing composite materials. 5,6 This method can fulfill both of the above objectives but it is currently laborious, expensive, and has the additional disadvantage that the volume fraction of reinforcing phase cannot be easily varied. On the other hand, unidirectionally solidified, two-phase alloys, also with a good bond between the phases, are relatively easy to make and the volume fraction of reinforcing "fibers" can be easily varied by changing the average composition of the alloy. The disadvantage of the cast alloys is that the mechanical effectiveness of the "elongated interdendritic reinforcements" (EIR)* may be reduced due to their rela- tively short lengths, the w factor in Eq. [2] of I. However, if the EIR have a high strength their contribution can be considerable. For composite materials containing discontinuous cylindrical fibers of various lengths the ultimate strength is given by1 where it is assumed that the composite fractures when the fibers fail. In Eq. [I], a, is the stress in the matrix just prior to failure of the composite, Vf is the total volume fraction of fiber reinforcing constituent, Vf(l+) is the volume fraction of fibers whose lengths exceed the critical length, I,, which is defined as the shortest length of fiber in which the stress can build up sufficiently to break the fiber. af is the fracture strength of the fiber material, w is a factor accounting for the discontinuity of those fibers whose lengths exceed I,, 1-/d is the average aspect ratio of those fibers whose lengths are shorter than I,, and t is the shear stress in the matrix at the fiber-matrix interface. The factor w is dependent on the length of the fibers and also on whether deformation of the matrix occurs plastically or elastically. However, for a given length of fiber, w is smaller when elastic deformation of the matrix is assumed.' It is of interest to consider the properties of simple unidirectionally solidified, two-phase alloys at elevated temperatures in view of the possibility of using suitable modifications for high temperature service. Knowledge of the creep behavior of these materials is still rudimentary (although under active investigation) and the present paper concerns itself with short time tensile properties of some alloys similar to those investigated in I (i.e., unidirectionally solidified Al(rich)-Cu alloys). Unidirectionally solidified alloys containing 5.6, 17, and 23 wt pct Cu were tested parallel to the direction of solidification at temperatures from 25" to 500°C. In the present investigation, the alloys were homogenized for 2 days at 535°C giving a matrix of homogeneous a phase (5.2 wt pct Cu) and an interdendritic constituent (EIR) which was completely Q phase (53 wt pct Cu). EXPERIMENTAL Alloys of nominal composition 5.6, 17, and 23 wt pct Cu (containing approximately 0, 17.5, and 27.7 vol pct 8 phase, respectively, after homogenization at 535°C) were prepared by melting 1200 g of A1 (99.99 pct) in a high purity graphite crucible and adding the appropriate amount of freshly cleaned copper chips (99.9 pct). The molten alloy (at 700°C) was poured into a preheated graphite mold (also at 700°C) and the ingot unidirectionally solidified by impinging water on the steel baseplate of the mold. The alloy was degassed immediately

Jan 1, 1970

By G. A. Zeito

Detailed visua1 examination of outcrops was used to ob-tain data on the lateral extent of shale breaks. Thirty vertical exposures belonging to maritie, deltaic and channel depositiorral environrrrents were exatmind, surveyed and photographed. The dimensions of the outcrops ranged from 356- to 8,240-ft long and 25- to 265-ft thick. Shale breaks were found to extend laterally for significant distances. and in some sands terminates by joining other break v much more frequently than by disappearance. Consequently with regard to flaw, a gross sand consisted of both continuous and discontinuous subunits. The degree of continuity of shale breaks as well as the occurrence and spatial distribution of discontinuities were different for the three depositional environments. Statistical eva1uations were performed to determine the confidence level with which estimates derived from outcrops can be applied to reservoir sands. Results of these evaluations revealed that: (I) the lateral continuity of shale breaks in marine. sands is si~nificatit, and the estimates of lateral extent can he applied to reservoir sands with a high degree of confidence (80 to 99 per cent of the shale breaks continued more than 500 ft, with a confidence of 86 per cent); and (2) the tendency for adjacent shale breaks to converge upon each other over small distances in deltaic and channel sands is highly significant (62 to 70 per cent of the shale breaks converged in less than 250 ft, with a confidence of 50 per cent), hut the probable magnitude of the resulting sand discontinuities cannot yet he predicted with adequate confidence. INTRODUCTION Almost all of the efforts devoted to characterization of the variable nature of reservoir sands have been focussed on permeability variations. Among the widely used concepts that have emerged from these efforts are those of stratified permeabilities, random permeabilities, and communicating and noncommunicating layers of different permeabilities. This study is concerned with the presence of interbedded shales and silt laminations. These features are impermeable or only slightly permeable to flow. Therefore, knowledge of the extent to which they continue laterally and the manner in which they terminate within the bodies of gross sands is important for proper description of reservoir flow. Initial field observations made on outcrops revealed that shale breaks and the relatively thinner silt laminae have impressive lateral continuity. They appeared to divide sand sections into separate individual sand layers. Although most of the layers were continuous across the total lengths of the outcrops, some were discontinuous because the- bounding shale breaks converged. Furthermore, the discontinuous layers appeared more prevalent in channel and deltaic sands than in marine sands. Based on these initial findings, a detailed investigation was carried out to determine, quantitatively: (1) the degree of continuity of shale breaks in marine. deltaic and channel sands; and (2) the frequency and spatial distribution of discontinuities in the three environments. PROCEDURE The procedure used to obtain field data from outcrops included visual examination, surveying and photographing each outcrop. The photographs were examined carefully and important outcrop features were traced, measured and recorded. The selection of outcrops for this study was made on the basis that each outcrop should be exposed clearly to permit detailed visual examination of vertical lithology. and it should also be sufficiently long (over 200 ft) to provide useful data on the lateral continuity of lithology. Identification of the depositional environment for each outcrop was made on the basis of bedding characteristics, vertical sequence of lithology and the presence of indicative sedimentary features. Whenever possible, hand specimens of associated shales were collected to determine depositional origin. Almost one-half of the outcrops used in this study required environmental identification; the remainder had already been identified by previous investigators. Several photographs of each outcrop were usually required to cover the entire length of the outcrop. These photographs were taken from one station or several, depending on the terrain, size of the outcrop and distance to the outcrop. A Hasselblad camera, with a standard 80-mm lens and a 250-mm telephoto lens, was used. The telephoto lens permitted photographing outcrops as far as two miles away. Slow-speed films were used. either Panatomic-X or Plus-X. The final operation conducted in the field was that of surveying the outcrops. The distance of an outcrop from a point of observation was determined by a triangulation method using the plane table. The measured distance was then combined with the angle of view of the camera lens to establish a scale to be used on the photographs. Films were processed using standard processing techniques and 4.5X enlargements made. The enlargements of each outcrop were butted together to form a single panorama. Slides were also prepared on several outcrops; these were used whenever greater magnification (wall projection) was required to bring out maximum lithologic detail. The shale breaks and bedding planes in each outcrop were traced on transparent acetate film superimposed on

Jan 1, 1966

By M. J. Marcinkowski, K. S. Raghavan, A. S. Sastri

A detailed transmission electron microscopy investigation was carried out in connection with a manganese Hadfield Steel. At small plastic strains, numerous individual intrinsic stacking faults are observed. With increased plastic deformation, the stacking faults thicken into twin lamellae which in turn subdivide the original austenite matrix into smaller domains. The twin boundaries act as strong barriers to subsequent dislocation motion and is in a sense equivalent to grain refinement. It is this "grain refinement" which is believed to be the cause of the very high work hardening rates in the Hadfield Steels. In many cases, especially where an hcp phase is the stable one at low temperatures, the stacking fault energy in fcc metals and alloys decreases with decreasing temperature.' Since stacking faults of the intrinsic type are precursors of both twins as well as the hexagonal close packed structure, both of these entities should become more frequent as the temperature of a fcc crystal is lowered. In the case of the twin, there is no chemical driving force for its formation and it is generally necessary to provide the required driving force by an applied stress, i.e., strain energy. In the case of the hcp structure the transformation from the fcc modification can occur spontaneously (marten-sitically) since a decrease in chemical energy does in fact occur; however, an applied stress will provide an even greater driving force toward complete transformation. Since the transformation products mentioned above occur in an inhomogeneous manner throughout the crystal and since these can act as potential barriers to further plastic deformation2 marked strengthening effects can be anticipated. Also because metal and alloy strenghening is in general proportional to the shear modulus, these effects should be greatest in steels of the austenitic type (y), i.e., the fcc types. Perhaps the two most important steels in this category are the austenitic stainless steels and the Hadfield manganese steels. Both may be quenched from elevated temperatures so as to retain the austenitic states characteristic of those temperatures. The effect of subsequent deformation at lower tem- peratures has a profound effect on the stress-strain curves of these alloys. In particular Fig. 1 shows the compressive stress-strain curves obtained with an 18-8 stainless steel which was quenched from 1850°C after annealing for 1 hr so as to produce all y. As the temperature is lowered, the work hardening rate increases markedly. Although some hcp or c mar-tensite can be generated by plastic deformation as the temperature is lowered,~ it is believed to be a transition phase4 and most of the martensite produced is of the bcc or a variety.3 It is this stress induced martensite which gives rise to the very low initial work hardening at 77°K as can be seen in the stress-strain curve in Fig. 1. Similar low initial work hardening rates have been observed in the stress induced Ni-Ti martensites.5 Fig. 2 shows that an even more rapid rate of work hardening occurs in the Hadfield steels treated in the same way as that described for the 18-8 stainless steels a; the temperature is lowered. It is this ability to work harden to such high stress levels that makes the Hadfield steels particularly suitable for armor plate and heavy construction equipment. However, unlike the case of Fig. 1, no initial low rate of work hardening is observed in any of the curves in Fig. 2. Thus the stress induced formation of any low energy martensite phase in any significant quantity must be ruled out. This observation is in accord with the X-ray findings of Otte.~ On the other hand, small quantities of the E phase have been observed by other investigators using transmission electron microscopy (TEM) above Even more significant was the fact that large numbers of deformation twins were observed in the deformed Hadfield steels,678 which were postulated to be one of the reasons for the high work hardening ability of this class of steels.8 It is the purpose in what follows to discuss a series of experimental observations pertaining to the stress induced transformation in a Hadfield steel and to formulate a dislocation mechanism which adequately accounts for the observed results. EXPERIMENTAL PROCEDURE The stainless steel used to obtain the curves shown in Fig. 1 was of the AISI Type 303 containing approximately 18.0 pct Cr and 8 pct Ni. On the other hand, the Hadfield manganese steel used to obtain the curves shown in Fig. 2 contained between 1.00 to 1.25 pct and 11.5 to 13.5 pct Mn. In all cases the samples were in the form of compression cylinders 0.220 in. in diam and 0.370 in. long. Prior to testing the samples were annealed for a hr at 1050°C and rapidly quenched into a brine solution. This treatment was sufficient to preserve the y phase for subsequent testing at lower temperatures. All samples were compressed in an Instron testing machine using a cross head speed of 0.02 in.

Jan 1, 1970

By Y. A. Chang

Phase relationships in the system Cr-Si have been established based on the melting point, X-ray, metallo-graphic, and DTA studies. The three intermediate phases, Cr3Si, Cr5Si,, and CrSi,, melt congruently at 177V ± I@,Cr3Si, 1680"i 20°, and 1490" *20°C, respectively, while the fourth intermediate phase CrSi, melts peritectically at 1413" i 5°C to Cr5Si3 and a melt containing 51 at. pct Si. The temperatures and compositions of the four eutectic isotherms occurring in this system are given below: DTA and metallographic evidences indicate that Cr5Si, undergoes a phase transformation at 1505" i20°C. The high-temperature form of this phase could not be retained by the quenching techniques used in this study. TECHNOLOGICAL interest in the developing of composite systems, consisting of Sic on the one hand as a fiber-reinforced material and metallic substances such as chromium, nickel, or Cr-Ni alloys as a binding agent on the other hand, stimulated the present investigation of phase relationships in the binary system Cr-Si. Earlier works concerning this system have been evaluated and summarized by ansen and Anderko.' Their phase diagram was based mainly on the works of Kieffer, Benesovsky, and schroth2 and Kurnakov.~ According to these authors, the three intermediate phases Cr3Si, CrSi, and CrSi, all melt congruently at approximately 1730°, 1600°, and 1550°C. However, they did not agree on the compositional stability of the fourth intermediate phase between Cr3Si and CrSi. Later Parthe, Nowotny, and schmid4 determined the structure of this phase to be tetragonal T-1 type using the single-crystal method, and concluded that this phase had a formula of Cr5Si3. Since the compilation of Hansen and Anderko,' a new phase diagram for the system Cr-Si has been proposed by Elliott5 based on the works of Goldschmidt and rand,' Guseva and ~vechkin,~ and Trusova, Kuzev, and Ormont8 and the earlier works quoted by Hansen and Anderko.' According to this proposed phase diagram, all four intermediate phases have large ranges of homogeneity and all melt congruently. More recently, Svechnikov, Kocherzhinskii, and yupkog studied the system Cr-Si by the DTA-method. According to their findings, the three intermediate phases, Cr3Si, Cr5Si3, and CrSi,, melt congruently at 1700°, 1720°, and 1475"C, respectively, while the fourth intermediate phase, CrSi, melts peritectically at 1475°C to Cr5Si3 and a melt containing 50 at. pct Si. The temperatures and compositions of the four eutectic isotherms were found to be: In view of the discrepancies existing in the literature concerning the system Cr-Si, it was decided to rein-vestigate the phase relationships in this system. EXPERIMENTAL a) Starting Materials. Chromium disilicide and chromium or silicon powders were used in the present study to prepare the melting point and DTA samples. CrSi, was obtained by directly reacting cold-pressed elemental powders in an atmosphere of Hz at a temperature of about 1250°C. Chromium powder, purchased from Stark Chemical Co., had the following impurities in ppm: Fe, 200; Mg, 1000; and 0, 250; while silicon powder, purchased from the Welded Carbide Co., had the following impurities in ppm: Ca, 700; and Fe, 3500. b) Melting-Point Determination and Differential Thermal Analysis. Cylindrical melting-point samples of approximately 13 mm in diam and 30 mm in length with a rectangular groove in the center were prepared by hot-pressing of well-mixed powder mixtures in graphite dies. Before the melting-point determination, the hot-pressed samples were ground on a sand paper to remove any minute surface contamination of graphite. A small hole of 1 mm in diam, drilled on the center portion of the samples, served as a blackbody cavity for the temperature measurements. DTA samples approximately 13 mm in diam and 15 mm in length were prepared in a manner similar to the melting-point samples. Melting points were determined using the Pirani technique under a helium atmosphere of 40 psi. The design, performance, and operation of this apparatus have been described in detail by Rudy and ~ro~ulski.'~ The temperature measurements were carried out with a calibrated disappearing-filament-type micro-pyrometer. The measured temperature was corrected for losses from the quartz window of the melting-point furnace and for deviations from blackbody conditions of the observation hole. The procedure for temperature correction has also been previously described." The DTA method of Heetderks, Rudy and Eckertl' was also used to check any phase transformations of selected alloys in the system Cr-Si. It was not possible to make remated runs on the same sample once melt-

Jan 1, 1969

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By H. E. Mauck

The many factors that control bumping must be carefully studied for each coal seam where bumps occur, and specifications known to exclude bumping should be incorporated in the mining plans. This calls for complete knowledge of the seam's characteristics and its adjacent strata, and in many instances these characteristics are not revealed until the seam is actually mined. Pressure and shock bumps, the two general types, occur jointly and separately. In this discussion no differentiation will be made. Whether pressure or shock, they are treated as bumps, and both must be eliminated. Bumps in mines have occurred in several places throughout the coal fields of the world. A study of many of these occurrences indicates that geologic characteristics, development planning, and mining procedure have contributed. But more specifically, there are conditions usually associated with bumps: thickness of cover, strong strata directly on or above the seam, a tough floor or bottom not subject to heaving, mountainous terrain, stressed and steeply pitching beds, and the proximity of faults and other geologic structures. Mine planning should incorporate these known factors (not necessarily in order of importance): 1) Main panel entries should be limited to those absolutely necessary to ventilate and serve the mine. This reduces the span over which stresses may be set up that will later throw excessive pressures on barrier and chain pillars when they are being removed. 2) Barrier pillars should be as wide as practicable so that they will be strong enough to carry the loads thrown on them when final mining is being carried out. 3) Pillars should never be fully recovered on both sides of a main entry development if the barrier and chain pillars are to be removed later. The excessive pressures placed on the main chain and pillar barriers by arching of the gob areas can result in bumping when these barriers are being removed. 4) Full seam extraction is better accomplished by driving to the mine boundary and then retreat-drawing all pillars. If there are natural boundaries in the mine—such as faults, want areas, and valleys —retreat should be started there. 5) Pillars should be uniform in size and shape. The entire development of the mine should call for uniform blocks with entries driven parallel and perpendicular. Only angle break-throughs should be driven when necessary for haulage, etc. 6) For better distribution of rock stresses and reduction of carrying loads per unit area, both chain and barrier pillars should be developed with the maximum dimensions. 7) Pillars should be open-ended when recovered. If they are oblong, the short side should be mined first. Both sides of a block should not be mined simultaneously, but under no circumstance should the lifts be cut together. 8) Pillar sprags should not be left in mining. If they are not recoverable, they should be rendered incapable of carrying loads. 9) Pillar lines should be as short as practicable. (Three or four blocks are adequate). Experience has shown that rooms should be driven up and retreated immediately. The longer a room stands, the more unfavorable the mining conditions. This contributes to bumping. 10) Pillars should not be split in abutment zones (high stress areas lying close to mined out areas) and if slabbing is necessary, it should be open-ended. 11) Pillars should be recovered in a straight line. Irregular pillar lines will allow excessive pressures thrown on the jutting points. Experience has shown that the lead end of the pillar line can be slightly in advance. 12) Pillar lines should be extracted as rapidly as possible. This appears to lessen pressures on the line and render abutment zones less hazardous. 13) Extraction planning should call for large, continuous robbed out areas. Robbing out an area too narrow to get a major fall of the strata above the seam tends to throw excessive pressures on a pillar line. 14) Timbering in pillar areas should be adequate but not excessive. Too heavy timbering or cribbing is likely to retard roof falls and throw excessive weight on the pillar line. 15) Experience has shown that when pillar lines have retreated 800 to 1000 ft from the solid, bumps can occur. Because this distance may vary in different seams, impact stresses should be studied for each individual condition. In any event, extra precautions should be taken against bumps in this area. This list of controlling factors may or may not be complete. It probably is not, but it covers most of the problem's significant aspects. The question is whether or not bumping can be eliminated. The answer is that bumping can be minimized and possibly eliminated if these and other established factors are thoughtfully considered and incorporated in the mining and extraction plans. If a mine has already been developed or the pattern set so that little change can be made, then it will be necessary to adjust to the most nearly practicable system that can incorporate the known factors.

Jan 1, 1959

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand these has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of —200 mesh material in the final product markedly increases costs of de-watering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins. Wasting of coal in the -200 mesh slimes may account for a loss in washer yield equivalent to 2.0 to 2.5 pct of the raw coal input. With rising mining costs the value of such a loss is constantly increasing and a need for a better solution to the fines problem becomes more pressing every day. From an operating viewpoint, also, continuous removal of extreme fines from the washing plant circuit permits good water clarification practice, improving significantly the overall cleaning efficiency. The obvious desirability of recovering a commercially acceptable coal from washery slimes prompted U. S. Steel Corp. to investigate the merits of the Convertol process developed in Germany." Although this process has been used commercially in Europe for some time, little if any consideration has been given to its possible adoption in the U. S. until very recently. Fundamentals of the Convertol Process: In the Convertol process, droplets of dispersed oil are brought into intimate contact with the solids suspended in the coal slurry to be treated. This contact causes oil to displace the water on the surface of the coal by preferential wetting, or phase inversion, after which the coal particles are allowed to agglomerate in a manner permitting their re- moval from the slurry by centrifugal filtration. The clay and other particles of mineral matter suspended in the slurry do not have the affinity for oil the coal particles have. Consequently the oil treatment is preferential to coal to the extent that more than 95 pct of the oil used reports with the clean coal recovered. Figs. 1 through 3 will clarify the steps involved in the process. Fig. 1 shows the suspended material in the slurry to be treated, which is a thickened product containing 40 to 45 pct solids. Oil is now injected into the slurry under vigorous agitation to produce good oil to coal contact conditions, which result in preferential oiling of the coal particles. These coal particles are then permitted to agglomerate by gentle stirring in a conditioner to form flocs, as shown in Fig. 2. At this point in the process the agglomerated oiled coal can be washed and partially dewatered on a vibrating screen, as shown in Fig. 3. Finally, the washed flocculate can be further dewatered in a high-speed screen basket centrifuge or in a solid bowl centrifuge. Commercial Application of the Convertol Process in Germany: The original Convertol process was developed by Bergwerksverband zur Verwertung von Schutzrechten der Kohlentechnik, G.m.b.H., a German research organization controlled by the Coal Operators Assn. of the Ruhr Valley. The process as reduced to commercial practice in Germany' is shown in Fig. 4. In this process a thickened slurry (40 to 45 pct solids) mixed with a predetermined percentage of oil is fed from a surge tank to the phase inversion mill. After the phase inversion step, the slurry is usually discharged directly to a highspeed screen centrifuge. From 3 to 10 pct oil is used, depending on type of oil, size consist of coal to be recovered, and operating temperature. The top size of fine coal cleaned in Germany by the Convertol process is limited by the size of the openings in the centrifuge screen basket. Any mineral matter coarser than the basket opening, which is generally 60 to 80 mesh, must remain with the oiled coal. If the coal fines have been effectively cleaned down to about 80 mesh, the cleaning performance of the process is practically unaffected by the presence of coarse coal particles. However, since recovery of coal much coarser than 80 mesh is mow economical by conventional methods, it normally becomes more costly to allow substantial percentages of this coarse coal in Convertol process feed. Where the general plant layout does not permit effective cleaning of coal sizes down to 80 mesh or lower. there is some justification for a coarser Con-

Jan 1, 1959

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By J. W. Snavely

THE high tension belt conveyor is introducing a new and tremendously expanded era of low cost bulk material handling. High tension belt conveyors are generally those installations involving very long centers, high lifts, or drops, in which the belts are stressed up to their maximum tension values, and further, where the belt construction provides tension capacity far beyond what is possible with conventional belt constructions. With these high tension installations, the magnitude of the forces involved demands careful refinement of accepted design practice in order to achieve optimum balance of all factors. No attempt will be made to evaluate the relative merits of belt conveyor haulage with other means of transportation. For present purposes, it is assumed this has already been done in favor of belt conveyor. Neither will any attempt be made to evaluate the various conveyor belt constructions now available or to balance the advantages of various types of mechanical equipment. It is also assumed that the basic haulage information on which the conveyor design is based is accurate and complete. A sustained maximum, uniform load on the belt at all times must be achieved through proper feed control and the use of adequate surge storage to level the peaks and valleys of any varying demand for the material being handled. General Belt Capacity Considerations The belt conveyor capacity tables published by various belting and conveyor equipment manufacturers vary to a considerable degree, and the ratings given are quite conservative. Of necessity, these published ratings are based on the handling of average materials under average conditions. In applying a high tension belt, all possible capacity from the belt must be obtained in order to hold its width to a minimum and thereby limit the initial cost. Two factors are involved, loading to maximum cross section area and traveling at a maximum practical speed. Belt Loading: Proper treatment of the loading of the belt will result in maximum cross section to the load, and published capacity ratings can be exceeded, sometimes by appreciable margins. On the 10-mile conveyor haul used in the construction of Shasta Dam, California, although the rated capacity of the belt line was 1100 tons per hr, at times the system handled peak loads of 1400 tons per hr, almost 25 pct better than the rated capacity. One of the large coal companies has been able to exceed rated capacity by as much as 50 pct. Loading conditions which must be controlled are: 1. Large lumps must be scalped off and rejected or the load must be primary crushed before being placed on the belt. 2. The material weight per cubic foot must be accurate, must be known for all the materials being handled, and must be known for the complete range of conditions of the individual material being handled. Long centers and high lifts magnify small differences into serious proportions. 3. Uniform feeding to the belt is most important. Various types of feeders are available, which can be used to place a constant predetermined volume of material on the belt, or, where an appreciable range of material weight exists, through electrical control actuated by current demand, to place a predetermined uniform tonnage on the belt. One long slope belt in a coal mine in Pennsylvania is being fed at three separate stations with the controls so arranged that whenever the maximum load is going onto the belt from the first station, the other two stations automatically cut out. Whenever the load from the first station drops back, the other two stations again automatically cut in. 4. Careful design of the chutes and skirts is necessary to get the load centered on the belt with a minimum of free margin along each edge. Some free margin at the edge of the belt is necessary to prevent spillage, but if the load can be kept accurately centered, this free margin area can be reduced, and more material can be carried on the belt. What can be accomplished in this respect will vary widely, depending on the nature of the material being hauled. The chute and skirt design must also protect the belt. 5. The design of chutes and skirts should also get the load traveling in the same direction and close to belt speed, so that the load comes to rest on the belt as quickly as possible. The design of the chutes and skirts is worthy of careful study, and after a system is put into operation it should be experimented with to get the best results. Belt Speed: High belt speeds should be used in high tension work. Obviously, high belt speeds enable haulage on a narrower belt, reducing initial cost. The major portion of belt wear takes place at the loading point and around the terminal pulleys. The

Jan 1, 1952

By P. G. Nahin, A. Grenall, R. S. Crog, W. C. Merrill

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By W. C. Merrill, P. G. Nahin, A. Grenall, R. S. Crog

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951