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By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

John G. Tripp-—The concept of converting fuel deposits in-situ to useful forms of energy and chemical raw materials has important possibilities as a means of stretching out our fuel resources. The authors have worked in this field for years and in fact are among the pioneers in developing in-situ techniques based on underground electrocarbonization. Their efforts have aroused great interest in this subject and their contributions will undoubtedly gain even more significance as time goes on. The 4 to 5 billion tons of petroleum are proved reserves, that is, they are completely defined and could be produced economically with present methods of recovery. Reserves of coal, tar sands, and oil shale shown in Table I are not equivalent to proved reserves as the term is used in the oil industry. Incidentally, the 4.3 billion tons of oil shown in the tabulation is equal to about 28 billion barrels of oil and, therefore, presumably does not include reserves of natural gas liquids estimated at about 5 billion barrels. The relative comparisons would be more complete if these liquids together with the reserves of natural gas were included in the tabulation. It is stated in the report that production costs of the order of 10c per million Btu's could be expected from a large industrial electrocarbonization installation. The authors state that the operation probably could be operated successfully and at a profit. I would like to express my view that for the operation to be profitable extremely favorable conditions would have to prevail. For example, the coal seam would have to be thick and close to the surface in order to minimize drilling costs; the deposit should be dry and so situated that there would be little, if any, inflow of ground water; and the seam would have to be relatively gas tight to avoid excessive gas leakage. Notwithstanding the tremendous strides that have already been made, it is my hope that the authors plan to continue their development work. Experiments on underground electrolinking and initial carbonization at Gorgas, Ala., indicate a need for improved control over the operation. Subsequent examination of the underground system at Gorgas has shown that the gasification zone did not always follow a direct path between the electrodes. Undoubtedly the control of the in-situ thermal processes can be improved by further development work. With respect to the electrocarbonization of oil shale it may be well to point out that the cost of mining oil shale is estimated to be 50c to 60c per ton. These are low mining costs as compared to coal. Thus it would appear that there is less economic incentive for applying in-situ thermal methods to oil shale than there is for applying these methods to coal. As is the case with in-situ methods for petroleum, the product from the shale having the most economic interest would be liquid oil rather than gas. The authors point out that for distances up to several hundred miles it is cheaper to transmit energy as electricity than it is to ship energy as coal. This is a very important point, and with coal shipping rates rising periodically, it could prove increasingly important in the future. I believe that the authors deserve great credit for their outstanding work on underground electrocarbonization. The knowledge resulting from their efforts is of great value to our fuels technology. James L. Elder—The experimental work conducted by the authors on the electrolinking-carbonization of carbonaceous materials in situ is of great interest. The method is of great importance in the development

Jan 1, 1955

By W. D. Brown

Newell1 has shown that hydrogen is removed from steel in a vacuum at a temperature of 500° to 900° C. within 136 hr. Holm and Thompson2 also state that, especially when the hydrogen is high, the results obtained by extraction at 800°C. agree with those obtained by vacuum fusion. In this laboratory, an apparatus was designed (Oct. 1940) and used wherein the piece of steel was heated at 100°F. in a Torricellian vacuum (Fig. I). This vacuum was produced by raising and lowering a "leveling bottle or bulb" containing mercury. Extensive tests were made with this apparatus. The weakness of the procedure was the possibility of leakage of air into the tube around the rubber stopper at the bottom. The present plan is to raise and lower the mercury by applying vacuum from a mechanical pump, to the top of the tube and then to a bottle of mercury in which the bottom of the tube is immersed. The Apparatus The extraction is made in a Pyrex tube A, I in. i.d. It is drawn down at the top at N and an 8-mm. i.d. tube is welded on it. To this a Pyrex stopcock E, 4-mm. bore, is welded. The tube between N and E is preferably 8 in. long and is graduated in milliliters. The total length of A to the stopcock is 28 inches. Heat is supplied by a split-tube furnace. 0 in. long by 6 in. in diameter, hinged on the side. A short pyrometer couple P is inserted through the walls of the furnace. In use this is standardized by comparison with a standard couple in a I-in. tube, just opposite this short couple. In the I-in. tube A a glass rod R, flattened at one end, supports the sample S and the length of R is so adjusted that the sample is in proper place. (It may float in the mercury.) The tube A is inserted in a large rubber stopper to fit the bottle B and extends nearly to the bottom. It is so placed that the handle of the stopcock faces the operator. In this stopper also is a short tube D bent at right angles for the application of vacuum. Also in this stopper is an 8-mm. tube C reaching nearly to the bottom; this is bent so as to miss the heater and again bent to bring it in line with and as near as possible to the upper and reduced part of tube A. On this tube C is welded a 4-mm.-bore stopcock H. In order that the two tubes may be as near as possible, the handle of stopcock H faces the back, or is the reverse of stopcock E. The total height of II above the bottom is 28 in. As explained later, this is the pressure-measuring tube C. The bottle B is about half full of mercury. The mercury must cover the ends of A and C by about I in. when they are evacuated. By tees T and rubber tubing RT the tubes A, C and D, the latter through the three-way stopcock M, are connected to the vacuum pump. A sheet of asbestos at K prevents the stopcocks E and H from becoming so hot that they leak. A good grade of vacuum lubricant prevents leakage of E and H. In order to measure the pressure of the

Jan 1, 1945

By J. Kucera, J. Vreštál

DIFFERENT authors1 ' have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-'3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing's coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me'tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By W. I. Duvall

A brief review of the resonant frequency and ultrasonic pulse methods for obtaining elastic constants of rock samples shows that the equations for an iso-tropic elastic solid commonly used to calculate Young's modulus, modulus of rigidity and Poisson's ratio can result in appreciable error if the rock is even slightly anisotropic. Consideration of the equations that relate bar velocities and free medium velocities to elastic constants for orthotropic, transversely isotropic and isotropic solids shows that a combination of the two methods can be used to determine average elastic constants for a single sample of rock. The determination of elastic constants in different directions requires a large number of tests on oriented samples. The use of both the resonant frequency and ultrasonic pulse methods is recommended so that the determination of both Young's modulus and modulus of rigidity is independent of the determination of Poisson's ratio. The dynamic elastic constants of rock can be determined in the laboratory from measurements on small samples which may be in the form of right circular cylinders (diamond drill core). Either the resonant frequency6 or ultrasonic pulse method1 can be used to determine the longitudinal and shear velocities in the same specimen. The resonant frequency method provides a measure of the longitudinal bar velocity, V,, and the torsional bar velocity Vt; whereas the ultrasonic pulse method provides a measure of the free medium longitudinal velocity, Vp, and the free medium shear velocity, V, . The elastic constants (Young's modulus E, modulus of rigidity G, and Poisson's ratio v) are calculated from the density of the specimen, p, and one of the pairs of velocities by means of equations from isotropic elastic theory. For the resonant frequency method the equations are: It should be noted that Eq. 5 is derived from Eq. 4 and 6 and the relation between the elastic constants for an isotropic solid as given by the first part of Eq. 3. The in situ determination of dynamic elastic constants is accomplished by generating a complex seismic pulse in the rock and measuring the arrival times for the longitudinal and shear phases of the pulse at two distant points.5 From these travel times and the distance of the travel path both Vp and Vs are determined. The density of the rock is determined from samples in the laboratory, and Eq. 4 to 6 are used to calculate the elastic constants. These three methods involve the assumption of isotropy and perfect elasticity, and require the use of the relation v = (E/2G) - 1, which holds only if the elastic constants are the same in at least two directions. The calculation of v by means of Eq. 3 introduces considerable error, as a 1% error in V, and V, results in a 20% error in v. If frequencies for samples with a length-to-diameter ratio greater than four and a length greater than 8 in. are measured carefully, the experimental error can be kept to 1%. However, it is not unreasonable to expect that the variation in Vb and Vt with direction may exceed 1%. Thus, for even a small percentage of anisotropy the use of Eq. 3 can result in considerable error in v. The calculation of v by Eq. 5 also involves some uncertainty as a 1% error in Vs and Vp can result in a 6% error in v. By means of the pulse method both

Jan 1, 1965

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By C. S. Smith, L. H. Beck

KNOWLEDGE of the Cu-Zn constitution diagram was critically examined in 1944 by G. V. Ray-nor,1 who suggested the diagram reproduced in Fig. 1 as the best evaluation of available data. No pertinent work on the constitution has been published since that time, although a number of authors have discussed transformation kinetics and theory. Despite the large amount of work that has been done on the constitution of these industrially important and scientifically interesting alloys, minor uncertainties still exist. For example, it is still not possible to say definitely whether a two-phase region exists between the ordered and disordered forms of the 8 phase. A careful re-examination of the phase boundaries in this part of the diagram was therefore undertaken. Two methods were selected for the new investigation—quantitative metallography for the higher temperatures and precision lattice parameter measurement for lower temperatures. Because of the relatively narrow two-phase regions flanking the ß phase in these alloys, quantitative metallography is particularly suited for their examination, since the relative amounts of the two phases are very sensitive to their compositions. The method, however, is useless below about 350°C because of the inadequate resolution of the two constituents. Below 400°, however, the X-ray diffraction method is applicable, although it is of somewhat lower sensitivity in this system. The changes of composition that occur during quenching from above about 500°C entirely vitiate X-ray measurements at room temperature though they do not affect metallographic area measurements. The two methods overlap and supplement each other admirably. Both methods depend on the attainment of equilibrium composition of the two phases in a more or less intimate mixture and thus avoid the difficult problems of nucleation and long range diffusion involved in the conventional metallographic bracketing method. The alloys were melted from a master alloy made from re-electrolyzed cathode copper and Horsehead 99.99 pct Zn. Melting was done under a cover of either borax or charcoal and the alloys cast into a 7/8 in. sq graphite mold for the a-ß alloys or a 3/8 in. diam cylindrical graphite mold for the ß-? alloys. The a-ß alloys were rolled at 750°C to 5/8 in. sq; annealed for 24 hr at 800°C and quenched; then rolled and swaged at 200°C to 3/8 in. diam rods, annealed 24 hr at 200°C, quenched and cold rolled 2 pct reduction. This treatment was intended to obtain a small grain size and to produce many nuclei of the minor phase for growth on subsequent heat treatment. The unworkable ß-? alloys were given preliminary treatment by sealing in Vycor tubes in vacuum and annealing for 4 hr at 800°C followed by cooling in air. Samples of homogenized alloys were checked spectrographically for impurities, but the principal components were determined on samples subsequent to heat treatment. The impurities analyzed averaged approximately as follows: Ag, 0.0002 pct; Fe, 0.004; Si, 0.0008; Cd, 0.005; Mg, 0.0002; and Pb, 0.002. For metallography, samples of appropriate composition were cut into rods 5/8 in. long, sealed in pyrex tubes in vacuum and annealed for eight weeks at temperatures of 470°C and below, two weeks at 480°, 500°, and 600°C, and 4 hr at 700°C, followed by quenching in cold water. Temperatures were accurate to ±2°C. The cylinders were then machined to 8.7 mm diam and a slice weighing 1.5 g cut with a thin saw transversely from the center of each. This

Jan 1, 1953

By M. Cohen, P. E. Beaubien, D. Caplan

Addition of 1 pct Mn to Fe-26 CY ca/(ses a12 increase in scaling rate at 870° and 1090°C. Whereas only the rhombohedral oxide, formrs on tire manganese-free alloy, with manganese present major amounts of the spinel .Mn0 . Pro-duced through which diffusion is more rapid. At 1090°C the scale formed OH Mn is highly, irregular due to blistering and sintering, This is a second cause of faster oxidation Since much of the blistered oxide does not participate as part of the protective layer. The oxide phases that form at different times depend on the degree to which the surface metal has become depleted, in manganese by preferential oxidation. PREVIOUS work has demonstrated that the oxide scales formed on chromium steels at high temperature consist of both spinel and rhombohedra1 phases and may contain considerably more manganese, especially in the spinel phase, than is present initially in the alloy.' It has further been observed that a binary Fe-26 Cr alloy scaled less rapidly than an equivalent commercial steel and formed no spinel.' However, it is not established if manganese in chromium alloys actually promotes formation of spinel nor if it affects oxidation resistance. It seemed expedient to try to evaluate the specific effect of manganese by oxidizing an Fe-26 Cr alloy containing a small manganese addition under the same experimental conditions as used for the manganese-free alloy.' EXPERIMENTAL Table I shows the composition in weight percent of the Fe-26 Cr-1 Mn alloy and of the Fe-26 Cr alloy used as reference. The alloy with manganese was prepared from the vacuum-melted Fe-26 Cr alloy by remelting in vacuum with the proper manganese addition. The ingot was rolled to strip and specimens 1.1 by 0.035 by 5 cm and 1.1 by 0.5 by 4 cm cut out or machined. As previously described2 the specimens were smoothed by abrading through 600-grit Sic paper, electropolished in acetic-perchloric acid (20 to 1) to remove 10 p of metal, annealed at 1100°C in 20 torr of purified argon, and electropolished to remove a further 10 p of metal. They were then either rinsed in water and methanol and blotted dry or immediately etched for 45 sec in deoxy-genated 4 N HC1 under cathodic polarization at 10 pa per sq cm. Oxidation runs were carried out in a vertical tube furnace in a flow of purified oxygen at 1 atm while the weight increase was recorded continuously on a* automatic balance.3 Alter 98 hr at 870.C or 20 hr at 1090"C the specimens were removed to flowing argon and observed microscopically for evidence of spalling as they cooled. Subsequently they were examined by X-ray diffraction, the oxides analyzed chemically, and metallographic cross settions prepared. RESULTS Figs. 1 and 2 show the oxidation curves of Fe-26 Cr-1 Mn at 870' and 1090C. The Fe-26 Cr reference runs are shown as dashed curves. Experimental details of the six runs are included in Table 11. The first 20 hr of run 1 is repeated in Fig. 2 to show the effect of temperature. At 8'70°C the weight gain for Fe-Cr-Mn is about twice that of Fe-Cr (curve 1 vs curve 2, Fig. 1). Both alloys show regular oxidation curves. On parabolic coordinates (right-hand scale of Fig. 1) the

Jan 1, 1965

By J. G. Y. Chow, S. B. McRickard

The tensi1e properties of Ferrovac iron have been studied from 4° to 300°K. The stress required for macroscopic yielding was found to he constant below approximately 50°K. The effect of mechanical twinning on this low -temperature stress plateau was investigated. The onset of twinning occurs in this iron between 130° and 150°K and depending on its previous thermal history the twinning-stress curue may drop below or remain above the vield-stress curves as the temperature is lowered. Twinning has been shown to initiate slip in quenclzed iron at low temperatures. In no instances, however, did the onset of twinning alter the continuity of the yield stress -tempwature curve. Our data shows that carbon inhibits twinning and slip at low tem-peratures. This observation nay be used to explain the ductile-to-brittle transition in iron. The effect of fast neutron irradiation on yielding and embrittlement in iron and Fe-C alloys is offered as supporting evidence for this viewpoint. THE mode of yielding in iron at low temperatures was studied in an attempt to find an expression based on a single mechanism to describe the thermal dependence of the yield stress of iron. There are two types of inflections observed in the variation of the yield stress with temperature in iron and Fe-C alloys. The first is associated with ductile behavior and consists of a region extending 50" to 100°K above absolute zero in which the yield stress is independent of temperature. The second is observed in more brittle materials such as Fe-C alloys and irradiated iron and consists of an abrupt discontinuity in the yield curve as the temperature is lowered through a ductile-to-brittle transition point. The temperature dependence of the yield stress for iron with four grain diameters as found in this study is shown in Fig. 1. To varying degrees all the curves appear to flatten or approach an asymptotic value as the temperature is lowered below 50°K. Several other investigators1,2 have observed a plateau in the yield stress of iron and steel at low temperatures and in 1956 Louat3 presented a theory which contained an explanation for this behavior. In a subsequent exchange with Erickson and Low4'5 who attributed the plateau to the onset of mechanical twinning Louat8 showed that twinning first occurs in iron and steel tested in tension at temperatures as high as 140°K which is well above the observed plateau in yield stress. Furthermore he pointed out that both twinning and slip are basically dislocation processes and that with modified parameters his original theory still applied when deformation is initiated by twinning. Variables which affect the ductile-to-brittle transition in iron are test temperature, strain rate, composition and grain size.7 LOW,8 Hahn et al.,9 and Hull10 have provided evidence which links brittle fracture at a given temperature with the specimen grain size and the onset of twinning. In fact, Hull equates the brittle fracture stress to the twinning stress. On the other hand brittle fracture has been observed in the absence of twinning and priestnerl1 has given a fracture criterion which is valid whether or not fracture is preceded by extensive twinning. The data presented here clarify the role of twinning in the low-temperature deformation of iron. Strong evidence is given that the amount and distribution of interstitial impurities such as carbon are of

Jan 1, 1965

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By F. W. Warnaars

The Los Bronces copper deposit is located on the west side of the Andes Mountains in central Chile about 54 km (34 miles) northeast of Santiago. The deposit consists of a hydrothermal breccia complex that was emplaced in the western part of an earlier porphyry copper mineral system. This system exhibits propylitic, sericitic, silicic to potassic hydrothermal alteration with disseminated and stockwork copper-molybdenum sulfide mineralization over an area of about 12 km2 (5 sq. miles). The Rio Blanco Mine, about 800 m (0.5 miles) east of Los Bronces, is an underground block caving mine located in the central part of this system. The mineralization at Rio Blanco is characterized by one of the highest primary copper grades known for porphyry copper systems. Present mining at Los Bronces is from an open pit located in the northern part of a hydrothermal complex that is composed of at least seven different copper-bearing tourmaline breccia pipes. Together these pipe form one large contiguous body about 2 km (1.2 miles) long and 0.7 km (0.4 miles) wide at the surface. This body crops out at elevations of between 3.5 and 4.1 km (2 and 2.5 miles) above sea level. Each breccia pipe has a characteristic shape, matrix, type and degree of mineralization and alteration. Quartz, tourmaline, specularite, anhydrite, pyrite, chalcopyrite, sericite, chlorite, and rock flour are present in significant quantities in most breccia matrices. The clasts consist mainly of quartz monzonite, andesite, and minor amounts of quartz latite porphyry. The seven different breccia pipes are identified, from oldest to youngest, as Ghost, Central, Western, Infiernillo, Fine Gray, Anhydrite, and Donoso. The breccias coalesce, interfinger, or display gradational contacts. In places they form sharp contacts with each other and with the surrounding intrusive or volcanic host rocks. Early breccias are disrupted or cut by subsequent breccia events. Explosive emplacement was followed by collapse after the release of hydrothermal pressures. The Los Bronces breccia complex has sharp contacts with the surrounding intrusive stock and andesites. These contacts dip inward on the north, west, and south margins. The eastern contact is nearly vertical and/or dips slightly outward and suggests a westward tilting of the body of about 15° after emplacement. The breccia complex is not fully explored at depth, but is known to extend at least below the 3 km (2 mile) elevation in its central eastern part, about 1 km (0.6 miles) below the highest breccia outcrop. Primary copper sulfide minerals are most abundant in the Donoso and Infiernillo breccias where the matrix consists mostly of tourmaline, quartz, sulfides, specularite, and/or chlorite with minor amounts of rock flour, sericite, and clay. The volume of the matrix material is mostly smaller than in the other breccias. Secondary enrichment enhanced the primary copper grade in the southern two-thirds of the Los Bronces breccia complex and in much of the surrounding porphyry system. Primary grades of 0.3% to 0.5% copper have been enriched to approximately 0.9%. This enrichment may extend from surface outcrops to a depth of more than 500 m (1, 640 ft) in more permeable parts of the breccia complex. A leached and oxidized capping of variable thickness covers a large part of the enriched layer and exceeds 300 m (984 ft) at one location. The shape and depth of the enrichment blanket and the capping suggest that the enrichment process is still active.

Jan 1, 1983

By S. F. Ravitz, S. R. Zimmerley

High-grade cobalt concentrates were produced from the complex Blackbird ore with very good recovery in continuous pilot-plant operations in which a low-grade bulk cobaltite-pyrite flotation concentrate was roasted in a multiple-hearth furnace to oxidize the pyrite selectively. The cobaltite was floated from the resulting calcine. THE existence of the cobalt-copper deposits in the Blackbird district, Lemhi County, Idaho, has been known for many years. However, these deposits have not yet been exploited successfully because of the low grade of the ore, absence of information on ore reserves, and lack of feasible methods for concentrating and recovering cobalt from the ore. In 1941, when it appeared that World War II might interfere seriously with imports of cobalt from overseas, the U. S. Bureau of Mines started an extensive mining and metallurgical investigation of the Blackbird deposits. Exploration by trenching and drilling1 indicated that ore reserves were adequate to warrant consideration of large-scale exploitation. A process for producing high-grade cobalt concentrates from the ore was developed at the Salt Lake City Station of the Bureau,2 and hydrometallurgical procedures for producing cobalt metal or oxide from the concentrates were developed at the Boulder City Station.3 The Howe Sound Co., through a subsidiary, the Calera Mining Co., carried out further exploratory work, which increased probable ore reserves to a tonnage commensurate with a large investment in mine, mill, transportation facilities, and refinery. Simultaneously, the metallurgical staff of the company, working in cooperation with the Bureau of Mines, further investigated the metallurgical problems. It was the opinion of both groups that pilot-plant testing was required to translate laboratory results into plant operation. In general, the Blackbird ore has a high content of pyrite and some pyrrhotite and contains 0.5 to 1 pet cobalt and 1 to 2 pet copper, which are present essentially as cobaltite and chalcopyrite. The copper can be recovered readily as a high-grade concentrate by selective notation. The cobalt then can be recovered as a bulk sulphide concentrate assaying 4 to 5 pct cobalt, but no satisfactory procedure for separating the cobalt from the pyrite and pyrrhotite directly by flotation had been found. The method developed by the Bureau for producing a high-grade cobalt concentrate is essentially an application of the old Horwood process of selective roasting.4 The bulk sulphide concentrate is roasted to form an oxide coating on the iron mineral particles, and the calcine is then treated by flotation. The oxide coating prevents the iron minerals from floating so that it is possible to obtain a high recovery of cobalt in concentrates assaying more than 20 pct cobalt. Laboratory tests by metallurgists of both the Bureau and the Howe Sound Co. had indicated the optimum roasting temperature to be 425° to 450°C. At lower temperatures the rate of oxidation of the iron minerals is too low, whereas at higher temperatures substantial quantities of cobalt are rendered water-soluble. Because of its high sulphur content (35 to 40 pct), the bulk concentrate tends to continue to burn after it has reached the optimum roasting temperature. Although excessive temperatures could be avoided in the small-scale laboratory furnaces, there was considerable doubt that the temperature could be controlled properly in industrial equipment. To provide material for the pilot-plant tests, the Calera Mining Co. installed a small, temporary flotation mill at the Blackbird property and treated

Jan 1, 1951

By S. C. Sircar, D. R. Wiles

The rate has been studied of the hydrogen reduction of nickel ions in acetate -buffered solutions, using a nickel catalyst. At temperatures between 130°and 160°C, the rate is found to be proportional to the catalyst area, the nickel ion concentration, and the hydrogen pressure. The effect of hydrogen ions is to reduce the observed rate, likely by causing the reverse reaction (dissolution) to proceed. The experimental activation energy was found to be 25 kcal per mole. THE precipitation of metals and lower oxides from solution by hydrogen reduction has been quite actively investigated during the past few years.1 In the case of nickel, the kinetics of the precipitation have been studied in ammonia solution2 but extension of this study to acid solutions has not attracted much interest, largely because of the unfavorable thermodynamics at all but the lowest acidities. For example, Schaufelberger foundg that only 10 pct reduction of nickel could be effected in sulphate solutions. One kinetic study of the reduction of Ni++ has been reported by Knacke, Pawlek, and Sussmuth,4 in which the order of the reaction was found to be one in nickel ion and one-half in hydrogen pressure. No mention was made as to the part played by the nickel catalyst, or by the pH of the solution. Moreover, the activation energy reported (4 .12 kcal per mole) is so low as to lead to some question as to whether diffusion might be playing a major role in determining the kinetics. We have recently completed a study5 of the kinetics of the hydrogen precipitation of nickel from acetate-buffered acidic solutions whose results confirm and amplify those of Knacke et al. EXPERIMENTAL PROCEDURES The work was done in a high-pressure autoclavee by the usual technique of removing small samples of the solution for analysis. Nickel analysis was done colorimetrically by the dimethylglyoxime method.' The catalyst used was carbonyl nickel powder (Standard A powder of the Mond Nickel Co., Ltd.) which was found to be composed of spheres of less than 350 mesh. The surface area of the powder was determined in this laboratory by the B. E. T. method to be 1.85 sq m (m2) per g. The catalyst was added to the solution only after the proper temperature and pressure had been reached. Agitation of the baffled system was by a turbine-type impeller, rotated at speeds between 400 and 750 rpm. The reduction rate was found to be independent of the stirring rate, so it was assumed that diffusion in the liquid does not limit the rate. In typical experiments, the nickel concentration was unchanged during an induction period of variable length. The concentration then decreased sharply, and gradually levelled off to approach the final equilibrium value. In some cases, notably at high stirring rates, the nickel concentration was found to increase considerably during the induction period, and then to decrease. In all cases, the rate was determined from the slope of the tangent to the rate curve as the concentration first decreased below the initial value. This is seen in Fig. 1. The rate measurements were found to be reproducible to within about 5 and to be quite independent of the nature or duration of the induction period. The range of conditions used is given in Table I.

Jan 1, 1961

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

P. W. BRIDGMAN.-Owing to a misunderstanding, I did not see Dr. McAdam's and Dr. MacGregor's remarks on my paper on Flow and Fracture (Metals Technology, December 1944, Pp. 32-38), until after their publication. Both Dr. McAdam and Dr. MacGregor speak of my analysis for the stress distribution at the neck of a tension specimen as containing several assumptions; in particular, that the strain is uniform across the section of the neck, that there is no hoop tension at the periphery, and that the plasticity conditions of von Mises hold. As far as the mathematics goes, the situation is no different in this problem of plastic flow than in a conventional problem of elasticity. That solution is unique which satisfies the boundary conditions on the stresses, the stress equations of equilibrium, and in addition the constitutive equations connecting stress and strain in the elastic case, or a corresponding set of equations, of which the von Mises relations are a special form, in the plastic case. In the particular case of the necked tension specimen I have found that there is a solution satisfying the boundary conditions, the stress equations of equilibrium, and the von Mises plasticity conditions in which the strain is uniform across the section, and there is no hoop tension at the periphery. This is therefore the solution, and the uniformity of strain and vanishing of hoop tension at the periphery are to be described as discoveries, over which the operator has no control, rather than as assumptions. The only part of the solution that can properly be described as an assumption is the von Mises plasticity condition. With regard to this it is to be noted that the condition is needed only in a much weakened form, for the analysis uses the condition only at the neck, where the strain is approximately constant. Thus, in the extreme case referred to in a footnote of my paper (p. 37, Met. Tech. Dec. 1944) the actually measured strain across the section varies from 2.4 to 2.6. Obviously it is a much weaker assumption to postulate that the von Mises condition holds in the strain range 2.4 to 2.6 than to assume it to hold for the entire range of strain from o up to 2.6, which would be necessary if the solution applied to the entire tension specimen rather than to the immediate region of the neck only. Furthermore, it is to be commented that under the special conditions of this problem the von Mises condition becomes identical with the maximum shearing-stress criterion of plastic flow; this amounts also to a weakening of the restrictions imposed by the von Mises condition. Dr. MacGregor refers to actual experiments of his own in which the strain was found not to be uniform across the neck. It is to be emphasized, however, that these were experiments on bars of rectangular section, and that the nonuniformity established was a nonuniformity around the perimeter, not a nonuniformity from the surface toward the axis. My method of solution applies only to a circular cross section. It can be said that the solution that satisfies the boundary conditions, etc., would definitely not be expected to demand a uniform strain for noncircular sections. In discussing my results, Dr. McAdam uses a definition of "flow stress" different from mine, so that the immediate applica-

Jan 1, 1945

By D. W. Frommer, M. M. Fine

Mineral dressing research showed that iron concentrates of commercial quality could be produced from the Pea Ridge deposit near Sullivan, Mo. Magnetic separation and flotation, on a laboratory scale, yielded concentrates ranging from 60.0 to 71.4 pet Fe at recoveries of 89.9 to 97.6 pct. Early in 1957 St. Joseph Lead Co. announced discovery of three new centers of iron ore deposition in east central Missouri.' The discovery resulted from exploratory drilling in the vicinity of a magnetic anomaly or high. A deep hole, drilled into the Pre-Cambrian porphyry to determine the cause of anomaly, penetrated a magnetite-rich deposit.' The magnetic surveys that revealed the anomalies were begun by the Missouri Geological Survey in 1929 and were continued into the 1930's.3 At that time an area in Crawford County known as the Bourbon magnetic high was located. A second anomaly, similar in size and intensity, was discovered about six miles to the northeast in Franklin County in the vicinity of Sullivan. This area was not studied in detail until the early 1940's. To determine the cause of the anomalies, the USBM drilled four holes at the Bourbon site in 1943-1944.4 The most productive hole penetrated four mineralized zones having a total thickness of 127.5 ft. These zones contained magnetite in rhyo-lite porphyry at depths between 1600 and 2000 ft. Additional iron ore below 2000 ft was considered a possibility at the time. Some years later, the USGS, Missouri Geological Survey, St. Joseph Lead Co., and others cooperated in sponsoring an aeromagnetic survey of the Bourbon-Sullivan area which resulted in discovery of a third high, about eight miles distant at Pea Ridge. This deposit, with an estimated reserve of 50 to 100 million tons of iron ore, is considered the main find, although other orebodies in the same general area are of definite interest.' When this discovery was announced, St. Joseph Lead also revealed plans to exploit the deposit jointly with Bethlehem Steel Co. A new corporation, Meramec Mining Co., was established, and 1962 was set as the target date for completing physical plant.2 Annual production goals of 2 million tons of beneficiated and pelletized iron ore were proposed. Preparation of the site for shaft sinking was begun in June 1957. Orebody and Character of Samples: Drilling to date has established the Pea Ridge orebody as a crescent-shaped pipe about 300 ft wide. Some drillholes were bottomed at 2800 ft in very good iron ore.6 he orebody is predominantly magnetite, although hematite and a mixture of hematite and magnetite occur in the upper areas and peripheral walls. Drillhole cores representing ore from different areas and depths of mineralization were grouped into composites for testing. These composites consisted of: 1) medium grade mixed hematite and magnetite, 2) high grade mixed hematite and magnetite, and 3) high grade magnetite. The medium grade ore came from three holes with depths of i350 to 1900 ft. The high grade mixed hematite and magnetite cores came from the 1790 to 2812-ft interval of one hole. Partial chemical analyses of the three samples, given in Table 1, reveal that all are excessively high in phosphorus and sulfur, and sample 1 is

Jan 1, 1960

By S. R. Zimmerley, S. F. Ravitz

High-grade cobalt concentrates were produced from the complex Blackbird ore with very good recovery in continuous pilot-plant operations in which a low-grade bulk cobaltite-pyrite flotation concentrate was roasted in a multiple-hearth furnace to oxidize the pyrite selectively. The cobaltite was floated from the resulting calcine. THE existence of the cobalt-copper deposits in the Blackbird district, Lemhi County, Idaho, has been known for many years. However, these deposits have not yet been exploited successfully because of the low grade of the ore, absence of information on ore reserves, and lack of feasible methods for concentrating and recovering cobalt from the ore. In 1941, when it appeared that World War II might interfere seriously with imports of cobalt from overseas, the U. S. Bureau of Mines started an extensive mining and metallurgical investigation of the Blackbird deposits. Exploration by trenching and drilling1 indicated that ore reserves were adequate to warrant consideration of large-scale exploitation. A process for producing high-grade cobalt concentrates from the ore was developed at the Salt Lake City Station of the Bureau,2 and hydrometallurgical procedures for producing cobalt metal or oxide from the concentrates were developed at the Boulder City Station.3 The Howe Sound Co., through a subsidiary, the Calera Mining Co., carried out further exploratory work, which increased probable ore reserves to a tonnage commensurate with a large investment in mine, mill, transportation facilities, and refinery. Simultaneously, the metallurgical staff of the company, working in cooperation with the Bureau of Mines, further investigated the metallurgical problems. It was the opinion of both groups that pilot-plant testing was required to translate laboratory results into plant operation. In general, the Blackbird ore has a high content of pyrite and some pyrrhotite and contains 0.5 to 1 pet cobalt and 1 to 2 pet copper, which are present essentially as cobaltite and chalcopyrite. The copper can be recovered readily as a high-grade concentrate by selective notation. The cobalt then can be recovered as a bulk sulphide concentrate assaying 4 to 5 pct cobalt, but no satisfactory procedure for separating the cobalt from the pyrite and pyrrhotite directly by flotation had been found. The method developed by the Bureau for producing a high-grade cobalt concentrate is essentially an application of the old Horwood process of selective roasting.4 The bulk sulphide concentrate is roasted to form an oxide coating on the iron mineral particles, and the calcine is then treated by flotation. The oxide coating prevents the iron minerals from floating so that it is possible to obtain a high recovery of cobalt in concentrates assaying more than 20 pct cobalt. Laboratory tests by metallurgists of both the Bureau and the Howe Sound Co. had indicated the optimum roasting temperature to be 425° to 450°C. At lower temperatures the rate of oxidation of the iron minerals is too low, whereas at higher temperatures substantial quantities of cobalt are rendered water-soluble. Because of its high sulphur content (35 to 40 pct), the bulk concentrate tends to continue to burn after it has reached the optimum roasting temperature. Although excessive temperatures could be avoided in the small-scale laboratory furnaces, there was considerable doubt that the temperature could be controlled properly in industrial equipment. To provide material for the pilot-plant tests, the Calera Mining Co. installed a small, temporary flotation mill at the Blackbird property and treated

Jan 1, 1951

By N. H. MacMillan, W. M. Mularie, R. E. Jackson, A. R. C. Westwood

The initial results of a study of the environment-sensitive microhardness and diamond rotary drilling behavior of granite and its constituent minerals quartz and feldspar (microcline)1 have established that many similarities exist between the environment-sensitive mechanical (chemomechanical) behavior of these materials and that of the simpler solids such as periclase, soda-lime glass, and alumina4 studied previously, at least as far as n-alcohol (straight-chain alcohol) environments are concerned. The results of this study (hereafter designated study I) also suggested that the rate of drilling of granite in these environments is controlled by the chemomechanical behavior of its quartz constituent, and is greatest in those environments which impart a zero l-potential to this phase, thereby maximizing its hardness. Now, cationic surface-active species strongly influence the l-potentials of silicate minerals. For this reason they are widely used in mineral separation operations. In particular, dodecyl trimethyl ammonium bromide (DTAB) was found in study I to produce f 0 for quartz at a concentration in water of 107 to 10-4 moles per 1. Accordingly, the influence of dilute aqueous solutions of this surfactant on the drilling behavior of granite also was examined in study I. This revealed that granite could be drilled three to four times faster in 10-° molar aqueous DTAB than in water, and confirmed by experiment the suggestion that granite is most effectively drilled with a diamond core bit in environments which impart a zero l-potential to quartz. According to O'Connor and Buchanan' however, the isoelectric point for quartz in aqueous DTAB solutions occurs at a concentration of .•.•2 x 10-° moles per 1, rather than [101 to 10-1] moles per 1. To confirm the results of study I, therefore, a more comprehensive investigation of the [ ]-potentials of quartz, microcline, and Westerly granite in aqueous DTAB environments has now been undertaken. At the same time an examination has been made of one of the basic assumptions of the current conceptual understanding of chemomechanical effects. In this view, although hardness changes occur essentially instantaneously following wetting of the solid, they are confined to a surface layer at most a few micrometers (µm) deep. Hence, to maximize the influence of chemomechanical effects on bit penetration rate only shallow cuts should be taken. Practical penetration rates are then obtained by increasing bit rotation speed. Experimental l-potentials were determined by the streaming potential technique using an automated rapid-cycling apparatus recently developed by Martin Marietta Laboratory from a design by Somasundaran and Kulkarni. The drilling studies employed 3.2-mm-OD 120-grit diamond-loaded core bits with a wall thickness of ~0.7 mm, and bit rotation speeds of 2200 and 25,000 rpm. The load applied to the bit was independent of the depth drilled in both cases. The 2200 rpm measurements employed the same drill press and puddle drilling technique as used in study I. The higher rotation speed was obtained using a water-driven dental turbine drill. In the case, the surface active fluid was pumped down the axis of the bit to ensure efficient wetting and flushing of the drilling debris from the hole. In both cases drilling rate was measured by the parameter D(200), defined as the average rate of bit penetration during the interval from 150 to 250 sec after drilling commenced.

Jan 1, 1976

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By R. Simon, L. Yarborough

This paper presents a correlation for predicting the critical pressures of gas-solvent-reservoir oil systems of the type encountered in gas and solvent injection processes. Experimental data from 14 systems were used to develop the correlation which expresses critical pressure as a function of composition, C7+ mol weight, and C7+ characterization factor. Critical pressures predicted by the correlation for the 14 gas-solvent-reservoir oil systems have an average deviation of 2.8 per cent of the experimental values. The correlation war used to study a wide variety of other hydrocarbon mixtures reported in the literature whose critical conditions are in the range of interest in oil recovery work (100 to 280F and 2,000 to 6,000 psia). Critical pressures predicted by the correlation had an average deviation, expressed as per cent of experimental value, of 5 per cent for 20 miscellaneous mixtures from the literature, and 6.4 per cent for I7 methane-butane-decane mixtures reported by Sage and Lucey. INTRODUCTION Predicting critical points of hydrocarbon mixtures is an important part of phase behavior calculations. If the critical point can be predicted for a specific mixture, the separation between the bubble-point and dew-point regions will be defined, and physical properties of the mixture can be calculated by using the principle of corresponding states. Numerous correlations for predicting critical points of hydrocarbon mixtures have been published. Six of these correlationsl-8 were for light hydrocarbons, and two correlations7,8 ere for high boiling-point petroleum distillates. Organick9 And Eilerts" presented correlations which combined the published data from both light and heavy mixtures, and these correlations became the only available methods for predicting critical pressures for wide boiling range mixtures. In the course of the authors&apos; work on secondary recovery by gas and solvent injection, experimental data were obtained for 14 mixtures of dry gas, ethane-propane-butane solvents, and various reservoir oils. The critical pressures and critical temperatures of these gas-solvent-reservoir oil systems were in the range of 1,900 to 4,800 psia and 180 to 265F. The critical pressures predicted for the 14 mixtures by the correlations of Organick and Eilerts had an average deviation from the measured values of about 13 per cent. The authors felt that it was necessary to develop a better correlation for engineering calculations and the resultant correlation, which is presented on Figs. 1 and 2, predicts the critical pressures of the 14 mixtures with an average deviation of 2.8 per cent. The validity of the correlation was tested by applying the correlation to other hydrocarbon mixtures reported in the literature. This subject is discussed later in the paper. The authors feel that there is also a need for an improved critical temperature correlation for gas-solvent-reservoir oil systems. However, developing a critical temperature correlation is a significant study in itself and is not included in this paper. EXPERIMENTAL DATA The compositions and critical points obtained by the authors for 14 gas-solvent-reservoir oil mixtures are shown on Table 1. The methane concentrations in these mixtures varied from 20 to 63 mol per cent. The intermediate hydrocarbon group, consisting of ethane, propane, and butane, varied from 20 to 64 mol per cent, and the concentration of the C,, fraction from 10 to 20 mol per cent. The physical properties of the C,, fraction covered the range from light, paraffinic, nonasphaltic (Mixtures 5, 6, 7, 8, 9 and 10) to heavy, aromatic, and asphaltic (Mixtures 13 and 14).

By A. G. Metcalfe

Observations at temperature are used to investigate the phase changes in alloys containing more than 50 pct Co and above 1000°C. The nonsuppressible transformations in cobalt above 1120°C and in the intermetallic compound Co2Cr3 are studied. The liquidus and solidus surfaces are determined. Insufficient data is obtained to complete the constitution diagram. A REVIEW of some of the earlier work on cobalt&apos; and on the binary systems with chromium2-4 and with molybdenum,5 showed that one likely source of differences might be attributed to the presence of phases at high temperatures which could not be retained by quenching. Consequently, the decision was made that only methods of examination at temperature should be used in this work. The correctness of this decision was confirmed during the course of the work by the investigation of the martensitic nature of the transformation in cobalt- and by the decomposition of the high temperature form of the phase Co2Cr3 on quenching.&apos; The use of high temperature methods, including dilatometry and thermal etching led to the postula-tion of the existence of a high temperature form of cobalt with a probable hexagonal close-packed structure, transforming from cubic cobalt over a range of temperature from 1119° to 1145°C.8 One of the important pieces of evidence for this transformation was that it was observed in alloys with chromium and molybdenum which were nonmagnetic at this temperature so that confusion with magnetostriction effects was impossible. These results were not reported in this earlier paper, so that the data given here supply further evidence for the existence of a second allotropic transformation in cobalt. High temperature observations are necessarily much slower in producing results than the examination of quenched specimens at room temperature by conventional means such as X-ray diffraction or microexamination. The investigation has only covered a limited part of the field, as a result, extending from the liquidus down to about 1050°C and from the cobalt corner up to 50 pct alloying elements. The differences between the various reported diagrams for the constitution of the Co-Mo and Co-Cr systems have already been mentioned. The best available diagram in the first system is due to Sykes and Graff&apos; which is shown in Fig. 1. Fig. 2 shows the latest Co-Cr diagram due to Elsea, Westerman, and Manning.&apos; A comparison reveals that these are incompatible because of the disagreement with regard to the number of allotropes of cobalt. Elsea, Westerman and Manning took their liquidus and solidus curves from Wever and Haschimoto.2 The temperature horizontal in the two-phase field beneath the eutectic was placed 35" to 39°C higher than in earlier work2,4 with a new interpretation of the nature of this transformation. This interpretation also required a peritectic horizontal at about 1470°C, which has been confirmed here for an alloy with 53 pct Cr. No investigation had been made of the ternary system until after this work had been terminated, when a section at 1200°C was published." In this work a ternary compound was found by the X-ray diffraction examination of quenched alloys. This compound contained less than 50 pct Co, and was thus outside the field investigated here. However, some reactions were found dilatometrically which could not be fitted on the diagram and are now believed

Jan 1, 1954