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By Rex W. Woods

The clue history of performance of a highly volatile type oil reservoir which is now greater than 80 per cent depleted is presented. The reservoir is at a depth of approximately 8,200 ft and includes an area greater than 7,500 acres. The reservoir has been exploited by 10 wells which to date have yielded about 10,880,000 bbl of stock tank oil by pressure depletion. Reservoir pressure has declined from an original of 5,000 psi to approximately 1,450 psi. Produced gas/oil ratio has increased from 3,200 to 23,000 cu ft/bbl with a corresponriing increase in APl gravity of the stock tank oil from 440 to 620 . Pressure and fluid data are given for different stages of depletion. INTRODUCTION In papers by Sloan,' and Cook, Spencer and Bo-browski,' properties of highly volatile type reservoir oil were discussed in detail and methods were presented for predicting performance of reservoirs containing this type of fluid. The purpose of this paper is to present performance history of a highly volatile type oil reservoir designated as Reservoir A which has been produced by pressure depletion and field separation without processing of gas GEOLOGY The reterence field which includes Reservoir A is a structural feature north of a trend of major folding along a northeast-southwest axis. In the area of development, the structure has the appearance of a dome with formation dip of three to four degrees, but structural relations between the reference field and the axis of major folding to the south have not been determined. No faulting within the field is evident. Oil and gas productive sands have been found at depths of 7,000 ft to 10,000 ft in a columnar section of Mio-Oligocene age. The sand bodies in the section are lenticular and usually continuity of sand is limited to a small area. Sand A which forms Reservoir A at a depth of 8,200 ft, however, has exceptional continuous development in the reference field. Fig. 1 shows an isopachous map of net oil sand for Reservoir A. Net thickness of oil sand at producing wells ranges from 14 to 34 ft with an average of 22 ft. Pinch-out of sand has been shown by drilling in the southwest part of the field, but extent of the reservoir on the northwest and northeast parts of the field is indicated only by thinning of the sand. The vertical oil column between the highest and lowest producing well in the reservoir is 339 ft. No water-oil contact has been found within the reservoir. As interpreted from the isopachous map, the reservoir includes about 8,900 acres with an average net sand thickness of 12 ft. Because of limited data on extent of the reservoir, the isopachous map permits only an approximation of sand volume in the reservoir. DEVELOPMENT AND PRODUCTION Reservoir A was discovered during 1938 and was developed with eight wells to the end of 1942. One well was completed during 1946 and the tenth well in the reservoir was completed during 1951. Three of the original wells and the last completion have produced from Sand A only. Six wells have produced from Sand A through the casing side of dual completions. Initial producing rates of the original wells ranged from 800 to 1,000 BOPD. Production history for the reservoir is shown in Fig. 2. Production of the reservoir was begun during 1940 and in May, 1952, peak production from seven wells was 5,300 BOPD. At the end of March, 1954. cumulative production was 10.880,000

Jan 1, 1956

By C. L. Thornburg

FLANKING the Valley of Mexico on the northeast is a mountain range known as the Sierra de Pachuca. This northwesterly-trending range is about 30 miles long and 5 miles wide, its summit attaining an elevation of more than 10,000 feet above sea level, or 2000 feet above the valley floor. Pachuca, a town of 50,000 inhabitants, lies nestled at the southwest base of the range, 60 miles northeast of Mexico City. Three miles to the east, just over the summit and on the northeasterly slope, is the mountain town of Real del Monte with a population of about 20,000. These are the two principal towns in a 40-sq mile area whose yield has brought the district to its high rank among the world's silver producers. Total production probably exceeds 1.25 billion ounces of silver and 4.5 million ounces of gold. Exploitation by the Spanish was under way by 1530. As the mines were deepened operations became handicapped by the inadequate method of handling water with horse whims and bull skins. To offset this disadvantage a two-mile drainage tunnel was started in 1749 and completed ten years later. John Taylor of London acquired the mines from the third Count of Regla in 1824 and formed the Compania de Real del Monte y Pachuca. Two years later Cornish pumps were brought from England. A Mexican company purchased the British interest in 1848 and within a few years resumed an old project of driving a second, lower three-mile drainage tunnel, completing it in 1857. After American interests acquired control of the property in 1906 operations expanded to an unprecedented scale, despite periods of political strife, unstable prices, labor problems, and a growing burden of taxation. An idea of the scale of operations may be gained from records of the last two decades prior to 1947, the last year for which production information is at hand, during which time production ranged from 1.4 million to 1.1 million tons per year, and the combined development and exploration, exclusive of diamond drilling, amounted to about 18 miles annually. Pachuca differs from Zacatecas and some other Mexican silver vein districts that flourished and declined in earlier centuries in that a substantial part of its total production was made after 1900. While the district's accelerated activity in this century was largely due to the successful application of the cyanide process to the treatment of the ores, improved pumping methods, and new mechanical equipment, it was at the same time stimulated by the opening up of important new orebodies as a result of active and extensive exploration of the vein system. Some of these orebodies were found on veins which terminate upward far below the surface, and though these particular veins do not crop out, they show relationship with a type of alteration which may be their surface expression. The district has been studied by many able geologists, and a large store of information has been accumulated, much of which is recorded in published as well as private papers. Wall Rocks Extrusive Rocks: The Sierra de Pachuca is a thick accumulation of Tertiary eruptive rocks consisting mainly of flows, breccias, and tuffs. Numerous recognizable volcanic vents within the range itself manifest that the range was built up by material ejected from these vents. The maximum thickness of the volcanic pile is not known, but from deep exploration and from relationship with Mesozoic sediments to the north and east it is inferred that the average thickness in the main part of the district may be at least 6000 ft. The extrusive rocks comprise four general types, which in ascending order of age are: andesite, rhyolite, dacite, and basalt. The veins are confined largely to the andesite, the dominant rock of the region. Characteristically this rock is augite andesite, but it includes comparatively acidic as well as basic layers, the acidic strata being

Jan 1, 1952

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

By Hisaaki Takata, Nobukazu Nanko, Ichiro Izawa

INTRODUCTION Tochibora Mine belonged to Kamioka Mines, which are located in Gifu Prefecture, the cen- tral part of the Japanese main island, has occupied the important position as a main source of silver, lead and zinc for the smelter of Mitsui Mining & Smelting Co., Ltd.. The annual production of crude ore goes up to about 1 mil- lion metric tons with average grades of 20g/t Ag. 0.31% Pb, and 4.18% Zn. For the last 20 years, the mine has struggled with the depressed zinc metal price in yen and the escalation of operating cost, especially la- bour cost. For instance, prices of commodities and labour cost have been raised 8 times and 14 times respectively during this period. On the other hand, total operating cost has been con- trolled to increase 4.5 times. The productivity of the mine has been increased 4 times by means of improvement of individual works and adoption of perfectly mechanized trackless mining system to reform the mining method. Some improvements are presented as follows; Today, drifting is carried out by the tunnelling crew which consists of 9 operators equipped with 5 Mobile-Jumbos, 2 LHD's and a jeep for carrying and loading ex- plosives. In order to get the high utilization of these machines, each crew manages systematically and continuously adjacent 15 faces under the direction of a forceman. As a result, we have accomplished high advance of drift. Furthermore, raising is carried out by a set of the raise-borer in case of long raises like ore- passes and also by the stage blasting method in case of short ones like slot-cuts. Generally speaking, the sublevel stoping method is considered to be one of the best methods for various respects; high productivity, low cost, easy grade control and safety. This method has been introduced in Tochibora Mine since 1950 and is now widely applied to lodes that could not be mined before by this method be- cause of the shapes of them and the conditions of their country rock. Now we are convinced to be nearly accomplished for our method. This report presents some examples of the standard sublevel stoping method and its variations which are practised at the mine. STANDARD SUBLEVEL STOPING Up to 1979 since 1950 when this method was first applied at the mine, 17 million tons of crude ore have been produced by this method, which amounted to 55% of the total production of the mine. During three decades, the productivity has been increased considerably by means of trackless mining system using large-sized machines and etc.. In other words, mining efficiency has been increased from 20 tons/man.shift to 100 tons/man.shift at large stopes. Formerly undercutting was carried out above the drawing drift by jack-legs and small scrapers and then several cone-shaped glory holes were made by stopers between the undercut level and the draw level. But now, a undercut drift is driven in parallel with the haulage drift at the same level of it. And at the undercut drift, drilling upward is carried out by a large-sized machines like the fan drill in order to extract the broken ore directly at the drawing drift connected with the haulage drift. Simplification of the work as well as utilization of large- sized machines enables to get higher productivity. But if the deposit is comparatively wider and the broken ore around the middle part of the deposit cannot be extracted, several drawing drifts are driven to the deposit and in order to minimize dead ore at the final stage of operation, the

Jan 1, 1981

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By W. M. Rutherford

A knowledge of the limits of miscibility between reservoir oil and possible injection fluids is required for selection of the optimum miscible-injection fluid. Limits of miscibility can be estimated from the results of equilibrium phase-behavior experiments. They can also be determined by means of displacement experiments conducted in a high-pressure sandpack. This paper describes the equipment and procedure which have been developed for determining miscibility conditions by stable displacement. A systematic series of displacements of a West Texas reservoir oil was carried out. The results indicate that, at constant pressure, miscibility is a function only of the pseudocritical temperature of the injection gas. This fact, together with improved experimental methods, makes the displacement technique a rapid, reliable means for determining miscibility conditions. In conjunction with the displacement experiments, phase diagrams were constructed for the oil with dry gas and propane and with dry gas and ethane. Phase behavior of the methane-ethane-propane system was determined at 110°F. The experimental work demonstrates the feasibility of using ethane-rich gases to reduce cost and pressure requirements for miscible displacement. INTRODUCTION In recent years, interest in the miscible displacement of oil by light hydrocarbon mixtures has been high. Many pilot and a few field scale projects have been started.1 These projects have made use of various methods for achieving miscibility: (1) the LPG-slug process, (2) the enriched-gas-drive process and (3) the high-pressure gas-drive process. Some field projects have been successful; the results of others are debatable. In general, projects which have performed best have involved the injection of an appreciable fraction of a pore volume of miscible material. Economical application of miscible displacement depends strongly on the cost of the miscible-injection fluid. If an appreciable fraction of a pore volume of material is required for successful application of these methods, a precise knowledge of the minimum requirements for miscibility in terms of composition of injection fluid is essential. Therefore, reliable experimental methods for determining miscibility conditions are important, and a procedure for estimating these conditions from the composition of the reservoir fluid is highly desirable. The subject of this paper is the problem of determining conditions which result in miscible displacement of oil by light hydrocarbon mixtures. Miscibility conditions can be estimated by means of equilibrium experiments conducted in a PVT cell, or they can be determined by means of high-pressure displacement experiments. This paper describes the equipment and procedure which have been developed for the determination of miscibility by high-pressure displacement experiments. These methods have been applied to the displacement of a West Texas reservoir oil with mixtures of dry gas, ethane and propane. In conjunction with the displacement experiments, triangular phase diagrams have been constructed for mixtures of the oil with dry gas and propane and with dry gas and ethane. The effect of injection-gas composition on conditions for miscible displacement in high-pressure sandpacks and cores has been the subject of several published papers.2-5 The experimental methods used in these investigations were such that displacements were unstable, and the effects of fingering and/or gravity layover are clearly evident in the results. Miscibility conditions were probably correct in spite of the instability phenomena, but the experiments evidently were time-consuming, and limited data were reported. Systematic high-pressure flow studies which would support a correlation of miscibility conditions have not been reported; however, Wilson5 has proposed the use of pseudocritical temperature of the injection gas as a parameter and Benham, et al,6 have based a miscibility correlation on observed and calculated equilibrium data.

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported'-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

By J. P. Hammond, C. J. McHargue, S. E. Adair

Cold-rolled sheet textures have been determined for binary solid solutions of aluminum, columbium, tantalum, and zirconium in titanium. An alloy containing 3.8 pct Al had a (0002) [10101 texture, whereas alloys with the other elements had rotated (0002) [10101 textures similar to that of iodide titanium. THERE have been relatively few studies of the effect of alloying on deformation textures. A second element may be present in the base metal in solid solution and/or as a second phase. The literature offers no satisfactory explanation for the effects of solid solution alloying on textures noted thus far. For example, there is no satisfactory explanation of the difference in the textures of copper and a brass. The most complete study of the effects of solid solution alloying on deformation textures has been that of Brick, Martin, and Angier.¹ These investigators reported that the copper texture was retained by alloys of copper with up to 30 pct Ni, less than 5 pct Zn, less than 2 pct A1 or Co up to the limit of solubility. Copper containing more than 5 pct Zn, more than 2 pct Al, or the maximum soluble concentration of tin, silicon, or manganese showed the deformation texture of a brass. Bakarian² reported that additions of 0.20 pct Ca to 99.98 pct Mg or 2.0 pct Mn plus 0.15 pct Ca to magnesium resulted in entirely different textures than for the pure magnesium. The texture obtained for high-purity magnesium sheet showed the basal plane to be concentrated parallel to the rolling plane. The texture obtained for the alloy containing 0.20 pct Ca had the basal planes concentrated in elliptical areas whose centers were tilted 15" from the center of the pole figure toward the rolling direction. This split basal orientation was even more pronounced in the alloy containing 2.0 pct Mn and 0.15 pct Ca. Fuller and Edmunds" studied the rolled sheet textures in a zinc alloy containing 1 pct Cu and 0.01 pct Mn. The basal pole figure of this alloy contained a region of strong concentration not found in the pole figure for pure zinc.' In the above cases, results were discussed in terms of possible changes in slip and/or twinning systems and critical shear stresses. However, there were no experimental data to relate these speculations with the observed textures. It has been suggested that the deformation textures of titanium, zirconium, and beryllium could be directly ascribed to their low c/a ratios. The complex deformation mechanisms of titanium" also have been suggested to be characteristic of hexagonal close-packed metals with low c/a ratios. The purpose of this investigation was to study the cold-rolled sheet textures in binary titanium-base a alloys in which the c/a ratios were greater than, less than, and about the same as the c/a for iodide titanium. The annealed textures of these alloys will be reported in a subsequent article. Materials and Methods The chemical analyses of the metals used in this investigation are given in Table I. The alloys were prepared as 15 g buttons on a water-cooled copper block in a vacuum arc-furnace. The furnace was evacuated to pressures of the order of 10.' mm Hg, flushed with 99.98 pct pure argon, and melting was carried out in 0.2 atm pressure argon. Each button was remelted until radiographs and chemical analyses indicated complete solution of the solute elements. All buttons were forged and homogenized 72 hr at 500°C. The buttons to be rolled were ground and etched to sizes and shapes suitable for the rolling

Jan 1, 1954

By Ronald J. McGregor, Anton R. Hendriksz

INTRODUCTION The NIMCIX contactor was developed in the late sixties at the National Institute for Metallurgy in South Africa, for the main purpose of extracting uraniuy from relatively low-grade uranium solutions. ' The concept was sufficiently developed by 1974 to permit the operation of a 1500 litre per minute column to treat unclarified urgnium-bearing solution under industrial conditions. The plant operated so successfully that several large-scale units have subsequent18 teen constructed and are operating efficiently. ' Total resin consumption figures as210w as 3 per cent per annum have been reported, and the extraction efficiencies of the installations have been exceptionally good. All the solutions treated have been acidic in nature and in every case have been of such a nature as to significantly depress the maximum uranium loading on the resin beads. The chemical constituents of the leach solution fed to the loading column determines the ease with which the soluble uranium can be absorbed by an ion exchange resin. The concentration of competing ions and various resin foulants define the nature of the continuous ion exchange equipment required for efficient extraction performance. The basic NIMCIX concept is retained in these various alternate designs, but batch or continuous elution methods with fully automated or manual control systems may be selected for the different process solution conditions. BRIEF DESCRIPTION OF THE NIMCIX CONTACTOR The NIMCIX ion exchange column is a multi-stage fluidized bed contactor which is designed to permit a counter-current flow of solution and resin in order to maximize extraction efficiency. The flow o resin is periodic, based on the Cloete and Streat 5 principle of reverse flow. The basic operating cycle can be divided into five periods, as illustrated in Figure 1. For the purposes of describing the cycle, the loading column is considered; how- ever, a similar sequence may be applied to the operation of a NIMCIX continuous elution column. S'I'EP 1: During the forward flow period, Solution flows up through the column and fluidizes the resin contained in each stage. The uranium depleted solution overflows the upper flared-section of the column as the tail solution. Step 2: The flow of solution to the column is temporarily stopped and the resin is allowed to Settle onto the plates in the column. STEP 3: During the reverse flow period, a fixed volume of solution is drained from the column to the transfer vessel. This flow causes resin transfer to occur from stage to stage and also out of the bottom stage. At the end of this period, which expires when the low level switch (LS) is actuated, some of the resin is left in the conical section of the column and the pipe interconnecting the column and the vessel. STEP 4: The cone flush period ensures that all the resin left in the cone of the column and the pipe is transferred to the transfer vessel before forward flow commences. STEP 5: The loaded resin in the transfer vessel, which has been isolated from the column, can either be hydraulically transferred to the top of the elution column or eluted in the vessel before being transferred to the top of the loading column. The major advantages associated with the NIMCIX concept are: (i) Simple method of operation (ii) Contactor can readily be scaled up to large diameters. (iii) Because the resin does not pass through pumps or airlifts, and valves cannot be closed on resin beads at any time, the resin losses are exceptionally low. (iv) Operating costs are low. (v) Relatively few valves in the system. (vi) Stable operation is achieved over a wide range of feed rates and concentrations.

Jan 1, 1980

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work' on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By H. M. Myers, J. E. Funk

The two-phase flow of a drilling fluid in a diamond drill bit is investigated by deriving and solving the steady-state continuity and momentum equations. Parameters in this analysis are rotational speed of the bit, local rate of addition of drill solids, non-Newtonian nature of the drilling fluid and drilling rate. The describing equations relate the flow and pressure drop to the design characteristics of the bit. The equations are integrated numerically yielding the flow-rate pressure drop characteristics for the bit, flow distribution in the bit and velocity and static pressure as a function of position in each flow channel of the bit. Results are presented for a particular bit design. This paper shows that under normal drilling conditions certain parameters may be neglected in the hydraulic calculations for a diamond drill bit. Therefore, shortened forms of the equations presented can be used to fit the proper diamond bit to the drilling fluid hydraulic system. INTRODUCTION Like the conventional bit, the diamond drill bit is a key component in the circulating system of a well. The conventional rock bit is fitted to the circulating system by selecting the flow nozzles which provide the system with the proper flow-rate pressure drop relationship. Fluid behavior across the face of the diamond bit must be better understood so the bit can also be fitted to the circulating system. Data from field-operated diamond bits are presently available and do yield some information regarding the flow-rate pressure drop relationship. However, the number of factors affecting this relationship is quite large. Drilling parameters and conditions such as bit penetration rate, bit weight and rotational speed are important. Moreover, flow channels in the bit are part of the cutting head, and introducing drilled solids into the flow channels reduces the flow area, causes additional drag and influences the pressure drop. Many tests would have to be performed if field tests were required to study all parameters which might influence fluid behavior in the bit. A logical approach to this problem is to investigate analytically the fluid behavior in the bit, including parameters that are present under normal drilling operations. This approach, which seems to offer the best method for future studies, is presented in this paper. Following is the general procedure. 1. Equations describing the most general flow channel are written and include the addition of drilling solids (which is related to penetration rate), rotation of the bit, design parameters of the bit and non-Newtonian properties of the fluid. 2. A typical bit is designed and the bit parameters are substituted into the equations. 3. Parameters are assumed (penetration rate, rotational speed of the bit, mud weight, etc.). 4. The describing equations are numerically integrated to obtain the pressure drop across the face of the bit as a function of flow rate. 5. The pressure-drop contribution of each component (friction, acceleration, etc.) is obtained from the numerical solution, and those factors which largely influence the total pressure drop are identified. Classifying the drilling fluid is important in establishing the friction factor relationship since the frictional pressure losses are the main contributors to the total pressure drop. High-density drilling fluid is commonly assumed to be a Bingham plastic. 1-3 Govier4 presented a method for selecting a friction factor in the laminar flow region from the rheology properties of the mud and a modified Reynolds number. Metzner5 presented a criterion for selecting the friction factor in the turbulent flow region. The bit design used in conjunction with the solution of the equations has divergent flow channels. Stall, which is the backflow of fluid in the channels due to eddies that occur on the outer perimeter of the flow stream, can occur in these divergent channels (or diffusers). When stall does occur the static

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By M. S. Hunter, D. L. Robinson

An extremely fine subgrain structure found in aluminum and aluminum alloys is shown and a method for revealing this structure is described. The appearance and some of the characteristics of this structure are described and the possible significance of subgrain structure in terms of chemical, electrochemical, and metallurgical processes is considered. GRAINS and grain boundaries, which constitute the principal manifestations of the crystalline aggregates known as metals, play such an important part in determining the characteristics and properties of metals and alloys that their nature and behavior have long been of much concern to the met-allographer. Many investigators have speculated on the possible existence of a finer structure within the usual grain structure and, through X-ray diffraction and metallographic techniques, have revealed evidence that such finer structures exist. Among these structures are the mosaic blocks and domains described by Burgers1 and others in their contributions on crystalline structure and the dislocation theory, the small units associated with polygoniza-tion described by Cahn,2 and the intragranular blocks revealed more recently by Lacombe and Beaujard.3 his paper describes some novel methods for clearly revealing a very fine granular substructure within the usual grains of pure aluminum and aluminum alloys. It also compares the characteristics and behavior of this subgrain structure with those of the ordinary grain structure and gives some examples of the manner in which this substructure may influence the characteristics of aluminum alloys. Metallographic investigations of aluminum and its alloys have dealt extensively with the functions and behavior of grains and grain boundaries and have evolved a definite concept of the relation between grain structure, orientation and physical, mechanical, chemical, and electrochemical behavior. During the examination of etched samples, a roughening or mottling of the body of certain grains has occasionally been observed. Such roughening obviously represented differential attack by the etching solution, but its true significance was not at first realized. It is now known that this roughening probably rep- resented a subgrain structure, although the particular etching treatments used were not capable of revealing this subgrain structure clearly. Also, in practically all cases, the subgrains were apparently far too small to be resolved by the light microscope. Recently, a method has been developed for revealing clearly the subgrain structure of most aluminum alloys. This method is somewhat unique in that it eliminates much of the usual tedious mechanical polishing and the attendant danger of a surface layer of flowed metal and at the same time is simple, rapid, and effective. It involves the use of the Alcoa R5 Bright Dip, a patented chemical polishing treatment licensed by Aluminum Co. of America. This treatment produces a bright, highly polished surface at least the equal of any mechanical polish and also etches the subgrain boundaries as well as the ordinary grain boundaries to reveal both the grain and subgrain structure simultaneously. Metallographic specimens to be examined are taken through the customary grinding and polishing operations used for aluminum alloys.' The usual care required in the final polishing operation to prevent a flowed surface layer and to obtain a high polish is not necessary, however, because any flowed layer is eliminated and a high polish is produced by the final immersion in the Alcoa R5 Bright Dip. Depending on alloy type, this dip takes from a few seconds to about 3 min, after which the sample is rinsed well, blown dry, and is ready for examination. The substructure can be revealed by some of the usual metallographic methods such as electropolish-ing or mechanical polishing and etching but no method has been found which is the equal of the new chemical polishing treatment. Mechanical polishing followed by the usual metallographic etching is not entirely satisfactory for revealing this substructure, probably because of the flowed surface layer resulting from the mechanical polish. If the usual etching methods are prolonged sufficiently to remove this layer, the specimen surface becomes quite rough and the substructure is not defined clearly.

Jan 1, 1954

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957