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By W. E. Bearce

The recent concern for the recovery of even the finest fractions of coal preparation plant feeds has created needs for new equipment. Thermal dryers currently available have difficulty reducing the filter cake moisture on down to the desired point. This difficulty involves 1) the physical problem of handling this wet, sticky material and making each particle accessible to the hot gases, and 2) removing the extremely fine dried particles from the cooled gases. The dryer described in this paper handles the first of these problems, and eliminates the second by the substitution of steel balls for air as the heat transfer medium. As a general statement, the cost of preparing coal for market is inversely proportional to the size of the lumps or particles. In the not too distant past the finer sizes were discarded as being uneconomical to treat and this practice might be still continuing if it were not for the insistence of the public that this material be kept out of our streams. This being the only cost-free outlet, the disposal of fine refuse became a significant item of expense in every preparation plant. When this happened it was only reasonable to look to the recovery of the values in this material, not only to defray this expense, but to reduce the tonnage which had to be wasted. There seemed to be no device available suited to reducing the moisture in this material to what the market requires. All of the fine coal dryers commonly employed make use of air to bring the heat of combustion into contact with the coal particles. Any device employing air as a heat transfer medium, has the following two strikes against it in attempting to handle 28 mesh by 0 filter cake: 1) It is practically impossible to bring the hot air into intimate contact with the enormous number of fine particles stuck together in the cake. 2) Even if this can be effected, it is impossible to remove the dried coal from the air. A wet scrubber must be employed, the discharge of which must go back to the filter and dryer as a circulating load of the most objectionable sort, being the extreme fines. Various compromises have been used to cope with the problem of drying this relatively small tonnage of high moisture coal. Often some of the dried coal is mixed back with the feed to the dryer in an attempt to make the mixture more handleable and more available to contact with the hot air than the filter cake alone would be. This may help to some extent with the first problem but it does nothing about the second and a dryer operated in this way has to be oversized. Sometimes the filter cake is mixed with a coarser fraction for the same reason. Here again, while this may make a mixture (the particles of which are more readily brought into contact with the hot air), the problem of getting the fine coal out of the air remains and a larger percentage of the total coal to be dried is handled by the most expensive means. Mechanical dewatering has accounted for more and more of total coal drying lately and in many cases would satisfactorily handle the whole load, down to 28 mesh, if there were a means available for doing a good job on the —28 mesh by itself. The dryer which is the subject of this paper was designed expressly for doing this job — drying fine material by itself regardless of how wet it may be to start with, how fine it may be, or how gummy and sticky these properties in combination may make it. The essential features are depicted in Fig. 1. A rotating cylinder is supported on a frame in such a way that one end may be raised or lowered by hy-

Jan 1, 1968

By R. L. Perrine

A stability theory is developed for miscible liquid-liquid displacement within a porous medium. In the usual case considered, a high-density high-viscosity "oil" is displaced downdip by a low-density low-viscosity "solvent'! Perturbation methods are used to find the conditions under which the spreading mechanism changes from the stable dispersion process to unstable viscous fingering. We find that instability is conditional, that there is a dependence on the shape of a disturbance leading to a"diameter" effect and that very difficult experimental scaling problems may result. A useful consequence is the definition of a minimum "slug size" for stable miscible displacement. This should make possible optimum use of the solvent process for oil recovery. The results may apply to many situations in which one fluid displaces another of somewhat different fluid properties within a porous medium. INTRODUCTION The process of miscible liquid-liquid displacement looked very favorable when it first received serious consideration as a means to increase petroleum recovery. Some early laboratory results were interpreted to mean that only a small "slug" of solvent was needed, perhaps 2 to 3 per cent of a hydrocarbon pore volume. This "slug" could recover the oil in an entire reservoir provided the fluids remained miscible.1,2 Only a slow growth of the "mixing zone", or gradual transition from oil to solvent, should occur. This would follow naturally from mixing by a dispersion mechanism such as that described by Scheidegger.3 And, indeed, laboratory cores have shown this kind of behavior provided solvent viscosity was at least as great as that of the oi1.2,4-6 The same kind of behavior has also been observed with solvent viscosity lower than that of the oil after the distance traversed became large. Not all laboratory results have been this favorable, however.7-9 Mixing zone growth may become proportional to the distance traveled rather than the square root of this quantity. Such behavior accompanies high rates in short systems of large diameter, provided the viscosity ratio is adverse. If this more rapid spreading were to persist in a reservoir, the solvent requirement for miscible "slug" displacement could exceed 30 per cent of a pore volume. There is considerable economic importance in the difference between 3 and 30 per cent solvent. A 1ogical conclusion is that two different kinds of flow behavior are possible, with each kind leading to a different result. One kind gives efficient displacement, the other does not. In the efficient case, the solvent bank spreads out only by the mechanism we have termed dispersion. Under these conditions, displacement is as near piston-like as possible. In the second kind of flow, found only with adverse viscosity ratios, viscous fingering occurs. That is, permeability variations cause a small finger of low-viscosity solvent-rich fluid to move ahead of its average position within the mixing zone. This creates a path of low resistance to flow, and an even greater amount of solvent-rich fluid follows. Thus, the process is autocatalytic. Once started, the fingering mechanism rapidly becomes dominant. The question to be answered is this. Under what conditions will each of these two different kinds of flow occur? In particular, what conditions denote the transition from dispersion to viscous fingering as the solvent spreading mechanism? The answer may tell us whether or not the desirable, near piston-like miscible displacement process is practical. An answer to this problem can be obtained from theory by the use of perturbation methods. The procedure is as follows. We first formulate a mathematical representation of the system. Then a small disturbance (or perturbation) in solvent concentration profile is introduced and observed to see what happens. Unstable flow is indicated when a small disturbance will grow larger. This will lead to eventual viscous fingering. If on the other hand the disturbance dies out, the displacement is stable. In this latter case, with dispersion as the spreading mechanism, near piston-like displacement is possible. Thus, this paper presents the development of a stability theory for miscible liquid-liquid displace-

By F. B. Plummer, I. W. Walling

Bastin and others have demonstrated the presence of sulphate-reducing bacteria in oil wells producing salt water. Analyses show that at 125°F. bacteria alone reduce sulphates in East Texas salt water by only 3 per cent in 30 days, forming principally hydrogen sulphide and sodium or calcium hydroxide. The hydrogen sulphide reacts with soluble iron compounds to produce iron sulphide in the absence of oxygen, and ferric hydroxide where oxygen and air are present. Where iron or other metals and iron sulphide are already in the water containing bacteria, I00 per cent reduction of the sulphates is complete in 30 days or less; where magnesium is present, reduction is complete in 15 days. The effects of changes in temperature, of different bactericides, and of concentration of bactericides on sulphate reduction are described in detail and illustrated by tables and curves. The significance of sulphate reduction on corrosive properties of oil-field water is briefly discussed. Chemistry of East Texas Oil-field Water The chemical composition of the water in the East Texas field salt-water disposal pits is shown in Table I. This salt water corrodes pipes, pumps, and steel tanks excessively, principally because of its content of oxygen, hydrogen, sulphide, and carbonic acid. The carbonates in the water when exposed to air tend to give up carbon dioxide and to precipitate calcium carbonate in large quantities. This forms coatings in tanks, settling pits, and ditches, and soon, unless removed by acid treatment, will effectively clog an injection well and reduce the flow of water back into the ground. The iron compounds in the water, most of which are dissolved from tanks and pipes, are in the ferrous form, and when exposed to the air are oxidized from soluble ferrous carbonate to insoluble ferric hydroxide, resulting in the precipitation of a gelatinous precipitate that will clog oil-field sands effectively: 2Fe(HCO3)2 + O + H2O -> 2Fe(OH)3 + 4CO2 The sulphates in strong sulphate-bearing water may be attacked by swarms of sulphate-reducing bacteria and more hydrogen sulphide may be produced. The hydrogen sulphide reacts with soluble minerals in the water to form black sludges. A knowledge of the chemistry of each reaction in oil-field water is important to the oil-field engineer, since means must be devised to prevent the formation of harmful precipitates that clog injection wells and to prevent corrosion of tanks by harmful products of biochemical processes. Methods of Treating Water before Injection into Ground* The open system of handling the waste salt water in the East Texas field consists of aerating and chemically treating the water to precipitate the unstable iron,

Jan 1, 1946

By J. T. Norton, N. J. Grant, A. R. Chaudhuri

MOST of the recent work to establish the mech-anism of creep in metals at high temperatures has utilized aluminum as the experimental material. It was thought desirable to initiate an investigation of a hexagonal close-packed metal, because of the relatively simple slip system, and compare the observed deformation characteristics with those that have been observed for the face-centerd cubic metals. High-purity magnesium was chosen for this purpose, first, because its strength and other mechanical properties are similar to those of aluminum in the same temperature range, and second, because the existing equipment was ideally suited to observe magnesium during creep. It is proposed in this paper to present a pictorial and qualitative account of the changes that high-purity magnesium undergoes during creep at 500°F. The characteristics of deformation of aluminum described below have been observed by various workers and accounts of these may be obtained from the papers of Chang and Grant.'- These characteristics are: slip, subgrain formation, grain boundary sliding and migration, fold formation, deformation bands, and kink bands. It is well known that in a flat magnesium specimen, slip on the basal plane (0001) in the [1120] direction results in the formation of straight bands on the surface of the specimen. Schmid and co-workers' have shown that this system is operative in the temperature range of -185" to 300°C (-300° to 572°F). They have also shown that a second system, slip on the pyramidal planes {1071} or {1012} in the [1120] direction, is operative at temperatures higher than 225°C (437°F). Between 225° and 300°C (437" to 572°F), therefore, deformation by both these systems is expected. Bakarian and Mathewson5 confirmed the occurrence of pyramidal slip on the {1011} plane and found that it resulted in irregular markings on the surfaces of their specimens. Burke and Hibbard6 obtained evidence of pyramidal slip in single crystals of magnesium deformed at room temperature. Bakarian and Mathewson5 suggested that the irregular appearance of these bands was due to slip on both of the pyramidal planes occurring simultaneously but in the same direction, the close angular relationship between the planes making this process possible. Furthermore, since neither of these planes is close enough to the basal plane, slip on the latter does not exhibit the irregular appearance of slip bands resulting from pyramidal slip. Experimental Procedure High-purity magnesium, supplied by the Dow Chemical Co., was used in these experiments. The analysis was as follows: Al, 0.0002 pct; Mn, 0.0018; Fe, 0.0024; Cu, 0.0002; Sn, 0.001; Ca, 0.01; Ni, 0.0003; Zn, 0.01; Pb, 0.0005; Si, 0.001; and Mg, 99.972. The magnesium was supplied in the form of 1/2 in. diam rods. The specimens had an overall length of 21/4 in., the round ends being threaded to fit the specimen holders. The previously round 3/16 in. diam gage section of the specimen had two parallel flats machined on opposite sides for microscopic observation, yielding a test zone having the dimensions of lx3/16x7/64 in. The specimens were electrolytically polished (without prior mechanical polishing of the machined flats), in a solution composed of 375 ml of ortho-phosphoric acid and 625 ml of ethyl alcohol.' The cathode was a stainless steel sheet bent so that the specimen was completely surrounded. The voltage for successful polishing was 1.5 v at 100 to 300 milli-amp current. Electropolishing for about 45 min sufficed to obtain a good metallographic surface on the specimens after they had been machined. The creep tests were performed under constant load, and two types of equipment were used. In the first, designed by Servi and Grant,V he specimens were beam-loaded, and a furnace could be lowered to surround the specimen. As the microstructural changes could not be observed during the course of the test, the tests had to be interrupted periodically by removing the specimen for microscopic examination. The second unit was a high temperature microscopy furnace designed by Chang and Grant.' The furnace was fitted with an optically flat quartz window having area dimensions 1.25x0.5 in., so that the whole test portion could be viewed through it at magnifications up to x240. The metallurgical microscope had three mutually perpendicular axes of motion, and, in addition, it was possible to measure angular displacements by rotation of the eyepiece. It was thus possible to make precise observations of the specimen during creep, and micrographs could be taken by attaching a camera to the eyepiece of the microscope. The average grain size of the specimens that were tested was about 1 to 3 mm. This grain size could

Jan 1, 1954

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.' on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-' (g S per sq cm)' corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.' The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By L. W. Holm, G. G. Bernard

Laboratory experiments were conducted to determine the effect of foam on gas flow in porous media. Previous studies have indicated that foam may be applicable as a restrictive agent in influencing underground gas flow. Foam was found to be exceedingly effective in reducing the permeability of porous media to gas. Consolidated and unconsolidated sands with specific permeabilities of 100 to 146,000 md had, in the presence of foam, gas permeabilities that were less than 1 per cent of the specific permeability; in many cases the gas permeability was practically zero. Foam reduced the gas permeability of loose sand to a much greater degree than that of a tight sand. For example, the permeability of a 125,000-md sand was reduced to 3 md while the permeability of a 4,000-md sand was reduced to 7 md. This effect should cause, to some degree, selective plugging of high permeability channels in various oil displacement processes. The presence of oil in a porous medium decreased the effectiveness of foam in reducing gas permeability; apparently oil acts as a foam depressant. However, it was found that certain foaming agents were very effective in reducing permeability even. in the presence of oil. Also, continuous injection of other foaming agents increased their effectiveness, when oil was present. The effect of foam on permeability of porous media to gas was studied as a function of foaming agent concentration and injection rate, absolute permeability, total pressure, pressure gadient, length of porous system, brine concentration and time. INTRODUCTION The use of surface active agents in flood water to increase the recovery of oil has been studied in the laboratory and in the field for decades, with rather limited success. In recent years a new approach to the problem was proposed. Instead of using an aqueous solution of surfactant as an oil recovery agent, Bond and Holbrook2 proposed that the oil recovery agent be a mixture of surfactant solution and gas. In their method, a water-soluble surface active agent with foam-producing characteristics is injected into an underground formation as an aqueous slug. This slug is followed by gas to produce a foam within the rock. Foams are defined as "agglomerations of gas bubbles separated from each other by thin liquid films'! A foam is fundamentally an unstable system. The foam process for oil recovery has since been studied by other investigators. Fried 1 has shown that foam can displace from porous structures oil that normally is unrecoverable by conventional water or gas drives. This superior oil displacing action is believed to be the result of several factors: (1) foam introduces into the reservoir many resilient interfaces of various sizes and curvatures, which increase the probability that a proper combination of forces for oil displacement will be created; (2) foam has appreciable viscosity which improves mobility ratio and contact efficiency; (3) foam accentuates the trapped gas effect because high gas saturations are possible without producing high gas/oil ratios. Deming4 studied the effect of various foam properties on the displacement of liquid. He found that (1) high foaming ability favors high displacement efficiency; (2) high foam stability is not necessary for high displacement efficiency; (3) displacement efficiency decreases with increase in plasticity of foam and (4) displacement efficiency is unaffected by surface tension of foaming agent solution. One of the important aspects of this oil recovery process is the effect of foam on gas permeability. The simultaneous flow of gas and liquid in porous media has been studied by numerous investigators and a large amount of literature exists on the subject. In this previous work, gas and liquid have generally been considered as essentially independent phases, whose flow characteristics are related through the saturation parameter. Foam, however, is a material with properties that are considerably different from those of its components; for example, the viscosity of a foam is greater than either of its components. Gas flow in a porous medium in the presence of foam should be considerably different

Jan 1, 1965

By R. A. Thomas, R. L. Solbod

The importance of transverse diffusion on the finger development in a miscible-phase displacement at an adverse mobility ratio of tbree was studied in a porous plate 1/4-in. thick, 3-in. wide and 18-in. long. Fast displacement rates (29 ft/D) and slow rates (1.6 ft/D) were used to determine the effect of residence time on the geometry of the fingers. The shape of the fingers was observed directly by use of the X-ray technique. At fast rates numerous narrow fingers were observed, but at slow rates a single somewhat bulging finger was produced. The amount of material moved transversely by diffusion across the plate was sufficient to modify the finger geometry in the slow-rate run because of the long residence time. These results are in contradiction to some of the postulates in the literature. The composition of the effluent stream, however, was not affected by the flow rate. This result is not inconsistent with the observed change in the shape of the finger in a short model, but it seems likely that a short model does not offer adequate and proper scaling of the reservoir. The model used was probably a valid one for studying the effect of transverse diffusion on the finger geometry, but a longer model would be needed for proper scaling of the effect of the change in the finger shape on the efficiency of displacement as measured by the composition of the effluent stream. INTRODUCTION Fingering can be defined as the uneven advance of the injected phase as it moves into a porous medium displacing the resident phase from the pore spaces of the rock. The use of this term is usually restticted to the situation in which the displacing phase is less viscous or more mobile than the fluid being displaced. Under these conditions, not only are fingers formed, but the length and width of the fingers grow with distance traveled in the porous medium. This subject has become one of great interest to the oil industry because of the present trend toward the use of various forms of miscible-phase displacement to increase oil recovery. Since in nearly all of the known modifications of the miscible-phase displacements an unfavorable mobility ratio exists (the displacing phase has a lower viscosity than that of the crude oil), the conditions are proper for fingering to develop. An appreciable amount of fingering appears to be a severe handicap to these processes for it increases the volume of agent required for the process to be a success, and such an increase puts a severe strain on the economics of the proposed processes. In some cases, such as for a mobility ratio of 200 unfavorable, it has already been demonstrated that the proposed process would not be economic if the fingering in the field were to be of the same magnitude as that observed in the laboratory. A number of aspects of fingering have been studied and reported in the literature. While the phenomenon of fingering cannot be regarded as a completely understood subject, considerable information exists on the effect of the path length and the mobility ratio on the growth of fingers. Less-complete data are available on the effect of the diameter of the flow path on the character and amount of the fingering, and even less agreement in results exists on the effect of rate of flow on the nature of fingering. This paper deals with one aspect of this latter subject. OBJECTIVE The objective of this study was narrowed down to one rather specific feature of the behavior of fingers in miscible-phase displacement in porous media. The variable studied was the effect of rate of flow on the nature and the development of fingers. It should be made clear at this point that, while rate was the apparent variable, the real variable was residence time; that is, at low rates the fluids are present at a given spot in the porous medium for a longer time interval than at fast rates. The purpose of the study, therefore, was to determine the changes which occur in the fingering and the possible benefits which might accrue from a longer residence time during that period when fingers are

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson&apos;s results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By A. G. Metcalfe, A. Siede

The hardening of annealed copper during fatigue testing appears to be independent of the applied stress and to occur largely within the first 4000 cycles. Copper hardened by fatigue is more resistant to annealing than copper hardened by static means, and softens by a multistage process. Creep studies at 300°C show that copper hardened by fatigue also has greater resistance to creep than statically hardened copper. Some theoretical explanations are discussed. RECENT interest in the behavior of metals subjected to fatigue stems from observations of phenomena which could not be explained by current theories of the structure of metals. In 1953 Bullen et al.l showed that the hardening caused by fatigue at low stresses did not cause severe bending of the lattice as did hardening by static methods. This was later confirmed by Wood, &apos;and Broom and Ham.3 Clarebrough et al4 showed that as the stress level used in fatigue hardening was increased, bending of the lattice was introduced, eventually approaching that of metals deformed by conventional cold-working methods. The type of hardening introduced by fatigue has other interesting characteristics. Kemsley5 showed that copper fractured by fatigue at low stresses resisted annealing as compared to copper hardened an equal amount by static means. The work of Clarebrough etal, shows that the manner of energy release during annealing differs for fatigue-hardened and statically hardened metal in both magnitude and temperature range of release. In addition to hardening of the lattice, fatigue has been shown to cause softening in materials previously hardened by static methods,5 and also in age-hardened alloys.7 The superposition of a small fatigue stress on the static loading of high-temperature alloys has been shown to increase their resistance to creep.&apos; The present work was an attempt to determine the relationship between fatigue hardening, resistance to annealing, and the creep properties of pure copper. EXPERIMENTAL PROGRAM The program described here was designed to answer three questions: 1) Can stress-cycle combinations well below the failure values give significant increases in hardness? 2) Does hardening, under different stress-cycle combinations, give increase resistance to annealing? And if so— 3) Does superior resistance to annealing confer superior creep properties over statically hardened material? Three-quarter hard OFHC copper was annealed in vacuo at 550°C for 1 hr to produce a strain-free material having a fine grain size and uniform hardness. (The standard deviation of the mean hardness of the annealed samples was less than + 1.9 Dpn). Annealing was performed after machining the fatigue specimens so as to avoid work-hardened surfaces. Jigs were used to avoid distortion. The fatigue properties of the annealed copper were determined using an accurately aligned Baldwin-Sonntag SF1-U machine operating at 1800 cycles per min. This limited the minimum number of cycles which could be examined to about 4000 stress reversals. Since failure resulted in specimen damage, hardness increase with number of cycles was measured by testing specimens fatigued to different fractions of the failure values. The results are shown in Fig. 1, and are superimposed on the S-N curve of the copper in Fig. 2. The resistance to annealing of fatigue-hardened material was compared to that of material hardened by uniaxial tensile straining. Specimens hardened to equal values by both methods were progressively annealed for 1 hr at temperature in vacuo. After each annealing treatment the hardness was measured using a Leitz Durimet hardness tester with a 500-g load. At least five tests were made for each hardness determination. The standard deviation for individual specimens varied from 0.26 to 1.48 hardness points. The results are shown in Figs. 3 to 5. The discontinuous nature of the annealing process has been brought out by drawing idealized curves through the data points. This can be justified by the consistency of the results as well as by general agreement with results of Kemsley.5 The creep resistance of fatigue-hardened and

Jan 1, 1960

By W. B. Gogarty

With the use of polymer solutions in secondary recovery operations, the need has developed to understand the mobility control mechanism. This study investigated mobility control by considering both permeability and rheological effects. Experiments used a high molecular weight, partially hydrolyzed polyacrylamide polymer. Flow studies took place in reservoir and Berea cores having zero oil saturation. Effective size of the polymer flow unit was inferred from Nuclepore filter tests. Clay studies indicated the particle size capable of decreasing the core permeability. Flushed permeabilities measured the approximate core permeabilities with flowing polymer solutions. These permeabilities were considerably lower than original values. With mobility data and the flushed permeability, maximum effective viscosities were determined for polymer solution flow in a core. Effective viscosities showed that rheological properties play an important part in mobility control with polymer solutions. The study showed that permeabilities decrease and stabilize with polymer flow. At the lower permeabilities, high shear rates exist in the cores. Because of the pseudoplastic character of the polymer solution, the high shear rates caused low effective viscosities. This condition pointed to the inefficient use of the potentially high viscosity of the polymer solution at low shear rates. INTRODUCTION In the oil industry, a great deal of interest is being shown in the use of polymer solutions for secondary recovery and a number of polymer floods are being performed in the United States.1 Some of these floods have become commercial while others have been reported as failures. A number of floods are still in progress and remain to be evaluated. With the advent of polymer flooding, the need developed to understand the mobility control mechanism in porous media. Rheologically, the polymer solutions behave as pseudoplastic fluids. Investigators have studied the rheology for this type of non-Newtonian fluid in porous media?-6 Results have also been reported on the ability of polymer solutions to decrease mobility.7-10 Some investigators indicated that polymer solutions show a different rheological behavior in cores than on the viscometer.7,8 This study is representative of an initiatory investigation on mobility control with polymer solutions. Some effects are considered on a qualitative basis. Mobility control is considered from the standpoint of both permeability and rheology and, to the extent possible, permeability and rheological effects are considered separately. Results show that mobility control occurs from a reduced permeability caused by polymer retention and an effective viscosity determined by the average shear rate in the core. In this respect, rheological behavior is as important in mobility control as permeability. PROCEDURES A high molecular weight, partially hydrolyzed, polyacrylamide polymer was used in the investigation. Solutions of various concentrations were made with this polymer in different types of water. Some solutions used distilled water and others used tap water. The tap water contained approximately 500 ppm dissolved solids. As used in this paper, concentrations in ppm refer to parts by weight solute to one million parts by weight of solvent. In the tap water, calcium and magnesium accounted for from 60 to 80 ppm of the solids, the remainder being mostly sodium chloride. All solutions contained a bactericide, and anti-oxidants and antiprecipitants were added to the tap water. Capillary and concentric-cylinder* viscometers determined the rheological properties of solutions. The capillary viscometer is described elsewhere.6 Berea and reservoir sandstone were used as core materials for this investigation. Cores were 1 in. in diameter by approximately 2 to 3 in. long. Prior to mounting, the Berea cores were heat-treated for 3 hours at 850F. This treatment decreased the water-sensitivity of the clays in the cores. The reservoir cores were cleaned with solvent and

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.&apos; The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.&apos; The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References &apos;P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

By H. L. Sauder, J. L. Newman, C. Waddell

An instrument capable of measuring subsurface flow rates is described. The instrument is self-contained and may be run on piano wire line. It detects flow by means of an impeller suspended between two torsion wires. The force of the well fluid striking the impeller causes the impeller to rotate, exerting a torsional force to the wires. This force is determined by recording the angle of rotation of the impeller on film using a battery-driven, clock-controlled camera. The impeller is sensitive to flow in either direction and the same instrument can be used to measure injection as well as production rates. Changes in direction of flow, such as might be caused by thief zones, are measurable and are indicated by a reversal of the direction of rotation of the impeller. Adjustment of the sensitivity of the instrument to measure a wide range of flow rates is accomplished by the use of different size torsion wires. An umbrella-type fluid trap, which contacts the casing or wellbore, diverts the flow through the flow tube. The fluid trap remains closed while rurrning in the hole and can be opened at any point in the well. The instrument with the trap closed is 1 3/4 in. OD and may be run through 2 in. tubing. Successful flow profiles have been made on wells with flow rates ranging from 60 BID to 4,000 B/D at surface pressure up to 4,500 psi. The instrument is designed for high-pressure and high-temperature operations. INTRODUCTION The need for an instrument that will measure flow rates in a wellbore is as old as reservoir engineering itself. A number of such devices have been designed within the past few years. Some of these have been described in the literature1,2,3,4,5,6 One of these devices1. a hot-wire anemometer type, made many successful jobs in dry gas producing areas. Difficulty was encountered when this flowmeter was used in wells producing liquids and development work was initiated to overcome this difficulty. The present flowmeter is the result of this work and provides an instrument with a wider range of application in the industry. Consider- able development work has been done on the tool involving many changes in the mechanics of recording the flow readings, however, the basic principle of flow detection has remained the same since its inception. PRINCIPLE OF OPERATION The basic principle of operation of the flowmeter is the utilization of a portion of the kinetic energy of flowing well fluid to impart a rotational force to an impeller suspended between two torsion wires. This impeller, Fig. 1, is a screw-type propeller with the blades having a pitch angle of 40. As the well fluid passes through the instrument it strikes the impeller. The resulting force rotates the impeller and twist\ the torsion wires to a balance point at which the torque imparted to the wires balances the force required for the impeller to deflect the well fluid. The impeller is symmetrical and a change in direction of the flow results in a reversal of the direction in which the impeller is deflected. Thus the direction of the flow as well as its velocity is indicated. A dial is attached to the impeller by means of a hollow tube through which the upper torsion wire extends. The angular position of the impeller is recorded by photographing the dial at frequent intervals. In any given set of torsion wires the modulus of shear and polar moment of inertia remain constant and the deflection varies directly with the applied torque. The deflection imparted to the torsion wires also varies as the square of the fluid velocity. Further, the velocities represented by any two given deflections hear the following relationships: and Where V = velocity of flow stream and O ;= deflection. This is the basic relationship which is used to calculate the relative velocities represented by a given set of deflections where the velocity represented by any one of the deflection readings is a known quantity. For a given torque, the deflection of the torsion wire varies inversely as the fourth power of the wire diameter. Wire sizes ranging from ,005 in. in diameter to .022 in. in diameter can be used. The range of

Jan 1, 1957

By J. B. Cheatham, R. B. Paslay

Rock stresses and steady-state flow rates induced by the pressure gradient associated with the flow of formation fluid into a borehole have been analytically determined for a permeable, elastic material saturated with an incompressible fluid. In this analysis, the material properties and loading are considered to be symmetric about the axis of the borehole and independent of axial position. For Case I the material is assumed to have uniform permeability in the radial direction, whereas for Case 11 the permeability is assumed to have been reduced in a localized region adjacent to the hole by either normal well completion and production operations or deliberate plugging during air drilling. Results of a numerical example indicate that, in the absence of plugging, the rock shear strength must be approximately two-thirds the formation fluid pressure in order to prevent rock failure. The required rock strength is high for small radial zones of plugging and decreases as the region of reduced permeability becomes larger; however, a depth of plugging can be reached beyond which there is no real gain in strength, although the flow rate can be further reduced. INTRODUCTION During normal production of oil from a well, it is often desirable to increase the production rate of the formation fluid by increasing the pressure gradient through the formation adjacent to the borehole. Depending upon the magnitude of this pressure gradient and strength of the rock material, this production-rate increase can cause sloughing of the hole wall. In many cases, the production - rate increase can result in excessive sand production, increased wear of production equipment, lost production time and expensive workover jobs. In addition, the phenomenon of increased rock bit penetration rate with the use of a gaseous instead of a liquid drilling fluid has been observed in oilfield drilling operations and experimentally demonstrated by various investigators for several years. The improvement obtained by employing this technique can be quite significant and offers apromising method for reducing drilling costs. However, air drilling is currently limited to geographical locations where high-capacity water-bearing formations are not encountered. This limitation has prevented widespread adoption of air-drilling techniques, because the water influx into the borehole interferes with efficient removal of the drilling cuttings and usually results in a condition such that the bit becomes "balled-up" or stuck in the hole. In an attempt to remove the water - intrusion limitation from air drilling, various chemical and mechanical water shut-off methods have been proposed. Goodwin and Teplitzl suggested one such proposal whereby the permeability of the water-bearing rock structure was reduced in the vicinity of the borehole. Although the development of a shut-off method based upon this approach would certainly be welcomed by the oil industry, it is conceivable that, under certain conditions of the pressure gradient, strength of the rock material and depth of the modified permeability zone, a stress field can be created that will result in an unstable hole. As part of their study, an analytical solution is given for stresses in an idealized model of a hole and the surrounding rock material. The purpose of the present study is to extend the analysis of Goodwin and Teplitz to gain more insight into the details and consequences of excessive production rates and formation water shut-off. In particular, simplified models of these problems have been analytically examined, which makes possible the evaluation of the type of stress fields that can be anticipated as a result of these production and drilling practices. Both problems solved concern the determination of the steady-state volume flow rate of the formation fluid and the resulting steady-state stress and displacement distribution in a hollow, cylindrical configuration. The cylinder of Case I, corresponding to the production-rate problem, consists of a material with a constant permeability from the inside surface to the outside surface; the cylinder of Case 11, corresponding to the water shut-off problem, consists of a material with a constant permeability from the inside surface to an intermediate concentric cylindrical surface and a second constant permeability from the intermediate surface to the outside surface-

By Matti J. Saarivirta

The relative machinabilities of the precipitation-hardenable Cu-0.9 pct Cr, Cu-0.25 pct Zr, and Cu-0.9 pct Cr-0.25 pct Zr alloys are improved from 18 to 80 pct by 0.75 to 1.25 pct Pb. The Lead also improves the tensile strength, hardness, ad resistance to softening of the Cu-Cr and Cu-Cr-Zr alloys. When the alloy containing 0.7 to 2.2 pct Cr, 0.10 to 0.25 pct Zr, 0.75 to 1.25 pct Pb, and balance copper is solution-annealed at 1000°C (1830°F) and then aged at 525°C (Y75°F), tensile strength of 65,000 psi, 16 pct elongation, 62Rb hardness, and 84 to 87pct IACS electrical conductivity are obtained. The copper base Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys have high electrical and thermal conductivities, high strength and resistance to softening at elevated temperatures, but their machinability is poor, i.e., close to that of the pure copper. In the manufacture of various components such as welding electrodes or electrical and thermal conductors it is ofter desirable that the alloy have good machinability for high production rates and long tool life. Thus, alloys that combine these properties may be used not only for existing applications, but for new ones where good machinability is a requirement. This investigation was undertaken to improve machinability without impairing other desirable characteristics of the Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys. These commercial alloys contain about 0.4 to 1.2 pct Cr, 0.10 to 0.25 pct Zr, and balance copper. Lead was selected as an element that should improve the machinability and possibly other characteristics of the alloy. WORK PROCEDURE This investigation began with a study of the effect of lead on the hardness, tensile strength, electrical conductivity, and machinability of the binary alloy containing 0.10 to 1.30 pct Cr and balance copper. This was followed by an investigation of the effect of lead on the Cu-0.1 to 0.4 pct Zr and Cu-Cr-Zr alloys. The alloys were made from initially oxygen-free copper and for comparison some castings were made from phosphorus-deoxidized Lake Copper. Commercially pure chromium, zirconium, and lead were used for alloying. In melting the chromium was added to molten copper at 1400°C (2550°F), the heat held for 15 min at temperature, and the temperature then lowered to 1350°C (2460°F) when the other elements were added. The alloys were held for 15 min at this temperature and cast into a cast-iron mold. One-kilogram, 3-in.-diam castings were made. An argon cover was maintained during melting and casting to prevent oxidation. The chemical compositions of the alloys are shown in Table I. The micro structure and properties of the alloys were studied in the cast and wrought conditions prior to and after various solution-annealing and heat-treating cycles. The relative machinability was determined as a function of the lead content and compared with the free-machining Cu-lpct Pb alloy. To determine the machinability, 13/16-in.-diam cast specimens were cut by a machine hack saw using a constant cutting speed of 50 fpm, a fixed feed force, and a new blade for each alloy specimen. Molybdenum highspeed steel saw blades, 0.032 in. thick with 14 teeth per in., were used in all tests. No cutting fluid was used. Five tests were made on each specimen and the average elapsed time per test was taken as a measure of the relative machinability for that alloy. The variation of cutting time for each alloy was less than 110 pct.

Jan 1, 1969

By R. D. Saltsman

This paper deals with the evolution of a test procedure devised to totalize a coal&apos;s ignitibility, its degree of caking, and its coke reactivity and the development of a method for assigning proper combustion indices to stoker coals. The application of this type of work to stoker design is also discussed. It is believed that this work may be the prelude to understanding the effect of various petrographic constituents on the combustion characteristics of a coal or a blend of coals. The inadequacy of our knowledge of the coal combustion process has long been recognized. This was expressed very well by Spicer and Finney.1 "The control of combustion processes in industry and the design of the equipment necessary for efficient burning to take place have always been very much branches of an industrial art rather than of an exact science. This has been especially true of the utilization of coal, a substance so heterogeneous and complex in character that all too little is known about its chemical and physical composition." During the past several years one branch of coal utilization, that of high temperature carbonization, has made significant advances from being an art into being an exact science. This has been accomplished by the development of petrographic techniques for identifying, measuring, and determining the thermal properties of the organic materials which affect the carbonization of coal and the correlation of this information with a pre-existing standard of coke quality, the stability index. The success in using petrographic analysis for predicting the coking properties of coals and their blends suggested that petrographic techniques might be applied to the combustion process for predicting the combustion characteristics of coals. Certainly the different organic entities2 influence the combustion characteristics of a coal as they influence its coking properties. If it were possible to predict combustion characteristics from an analysis of a coal&apos;s petrographic composition, it would seem logical that an intelligent investigation could then be made into methods of altering stoker coals to improve their combustion characteristics. The successful application of petrographic analysis in the field of high temperature carbonization was made possible by the pre-existence of the stability index, which is a numerical value of coke quality. The quality of combustion is determined by the sum of the effects of the ignitibility, the caking, and the coke reactivity characteristics of a coal. While the literature is filled with papers reporting the correlation of various analyses to the ignitibility, or to the caking, or to the coke reactivity characteristics of coals, none of these earlier studies could be related to one index. The lack of a single index for combustion quality precluded the application of petrographic techniques for predicting combustion characteristics. SELECTION OF THE COMBUSTION TEST EQUIPMENT The primary prerequisite of any test developed to evaluate the relative performance of stoker coals must reflect the three characteristics of the coal burning process: 1) ignitibility, 2) degree of caking, and 3) coke reactivity. The widespread variations in these combustion characteristics of the available stoker coals are well known. The ignitibility, which has been defined as that characteristic which determines the ease with which the fuel may be brought to a condition of self-supporting active oxidation, varies from where a coal is deemed to be flashy to the opposite extreme of being fireproof. The ignitibility of a coal influences its ability to pick-up from hold fire, greatly affects the degree of bed stability during swing loads, and is a factor in determining the average burning rate obtainable on a given grate. The caking characteristic affects the degree of bed porosity during the devolatilization period, and coals are classified on a scale varying from free burning to highly caking. Caking is not synonymous with bed swelling since a bed may swell two to three times its normal depth during the period of devolatilization yet remain very porous, allowing an efficient and high rate of combustion to take place. Caking is melting

Jan 1, 1964

By Didyk M. Marko, Vásquez Ñ. Gregorio

INTRODUCTION The Salvador Division of Codelco Chile is an important copper molybdenum production center, located 1,200 km north of Santiago and 124 km east of the Pacific Ocean, in the foothills of the Andes Range. El Salvador Mine produces by block caving 8,600,000 t of ore with a content of 1 .l0% Cu and 0.02% Mo, from a copper porphyry ore body. The geology of the ore body shows a great heterogeneity as to rocks, grade distribution, ore height and undercutting levels. This has resulted in a variety of designs for the productive units (blocks) and in the mineral handling systems. Up to now, 4 systems have been employed: grizzly and intermediate haulage; slusher drifts with intermediate ore pass and haulage; slusher drifts with scraper loading directly into trains; and, LHD. On the other hand there is a marked dispersion in the final results from each block mined out. We report here the conclusions reached after analyzing the data gathered on the mining of 163 depleted blocks, representing a total production of 102,000,000 t, with an undercut area of 340,000 sq m. The final results of each block, characterized in terms of tonnage and fine cop- per recovery, were studied as a function of a number of design, geological, and operational parameters. BASIC CONCEPTS Indices of Efficiency In order to evaluate the final result of each block, or group of blocks, the following indices of efficiency were defined : Tonnage Recovery (TR) . It is the ratio between the ore tonnage extracted and the in situ tonnage estimate for each block or group of blocks. Grade efficiency (E) . It is the ratio between the Cu mill feed grade and the in situ Cu grade estimate for each block or group of blocks. Grade efficiency is numerically equal to the ratio between fine copper recovery (FR) and tonnage recovery (TR) . Figure 1 shows the final results for 163 mined out blocks, in terms of tonnage and fine copper recovery. Different grade efficiencies are also indicated. The marked dispersion in the final results of mined out blocks must be stressed since it greatly incides in mine planning. It must be kept in mind that an eventual concentration of low overall efficiency in the blocks during a given period (e.g., one year) will make it necessary to bring into production new blocks over the standard development schedule. It is worth noting that the final results in the 163 mined out blocks corresponding to a production of 102,000,000 t of ore with a mill feed grade of 1.445% were obtained from an ore estimate of 93,000,000 t and a grade of 1.671% Cu, which represents 110% tonnage recovery and 86% grade efficiency. Parameters Studied The following parameters are considered in this study: Geological Parameters. These parameters depend exclusively on the geological and geotechnical features of the ore body. IN SITU GRADE: The initial estimate of the block grade. Four copper grade categories were considered : (a) lower than 1.3% ; (b) 1.3 to 1.6%; (c) 1.6 to 2.0%; (d) higher than 2.0%. The overall initial in situ estimate of the ore body was 1.6% Cu. IN SITU TONNAGE: Initial tonnage estimate of the block. Four categories are considered: (a) below 500,000 t; (b) 500,000 to 1,000,000 t (c) 1,000,000 to 1,500,000 t; (d) over 1,500,000 t. CONTACTS SLOPE: Since up to 4 rock types can be found in a block, resulting in a corresponding number of contacts, a horizontal con- tact was defined as that which forms an angle of less than 45" with the horizontal and a vertical contact that which forms an angle of more than 45" with the horizontal. GRADE DISTRIBUTION: As in rock types, horizontal and vertical grades were defined. ORE HEIGHT: The distance measured between the undercut level and the top of ore. Four categories are considered: (a) less than 60 m; (b) 60 to 100 m; (c) 100 to 150 m; (d)over 150 m

Jan 1, 1981

By S. R. Dunbas, D. C. Jillson, E. A. Anderson

THE present work was undertaken to furnish information, lacking in the literature, on the deformation mechanisms active in pure titanium at room temperature. Since it was started, Rosi, Dube, and Alexander&apos; have indicated that slip can occur in coarse-grained (2 to 6 mm diameter) titanium on the {1010} and {1011} planes and twinning can take place on the {1072}, (1122) and (1151) planes. Liu and Steinberg,&apos; working with titanium flakes produced by fused salt electrolysis, found evidence of twinning on the {1032$, {1121), {1122}, (1123}, and (1154) planes. The crystals used in the present work were substantially longer (up to nearly 2 in. in length) and possibly purer. Production of Large Crystals It was the purpose of this part of the work to provide single crystal or large grain specimens for use in the deformation studies rather than to study the mechanism of crystal growth. Accordingly, all further exploratory studies on methods were abandoned when it was found that cold-rolled bars sealed in vacuo in individual Vycor tubes and given three or more cycles of 4 hr at 1200°C and three to five days at 850°C, gave large grains. Eighteen specimens about 0.2 in. square x 2 in. long yielded 33 useful grains, ranging from Va in. to nearly 2 in. in length, with an agreeably wide range of orientations, Fig. l. The 0.25 in. thick strip from which the starting specimens were cut had been reduced 67 pct on 18 in. diameter rolls from a scalped, hot-forged (959" to 1000°C), arc-melted, iodide titanium ingot. Thc bar was at room temperature, but the rolls were at 200°C. Reductions of about 0.03 in. per pass were used. The bar was cut into four segments, each of which was rolled in a somewhat different manner. No effect on the growth of large grains was noted. The composition of the titanium, determined on turnings from the ingot scalping operations, is given in Table I. The Rockwell A hardness of the ingot was 26. The standard starting specimens, about 1/4x1/4x2 in., were milled on all four sides, hand polished on 280 and 400 mesh emery papers, etched for 3 min in a 50 HF-50 glycerine solution, rinsed, and dried in alcohol and ether just before sealing them in Vycor tubes. The average specimen weight was 7.5 g, and the tube volume was 6.5 cc. A vacuum of less than 1 micron pressure was applied. The specimen tubes were placed in an evacuated Inconel muffle to minimize the danger of collapse of the glass tubes at temperature. In practice the specimens were first heated to 1200 °C for 4 hr and then transferred fairly quickly to an 850°C furnace where they were held for three to five days. This cycle was repeated at least three times before the specimens were cooled, removed from the tubes, lightly polished and etched on one surface for examinstion. Those in which large grains had not developed were resealed in Vycor and returned to the cycling. Satisfactory specimens (about one out of every four cycled) were polished with emery paper on all four side;, then metallographically polished using ctchinz between wheels to remove distorted metal and, finally, given a very light etch to reveal the grain boundaries. This was necessary because the surface was roughened by the sublimation of titanium under high temperature vacuum conditions. Specimens were identified by TiXl numbers using supplementary letters to designate specific grains.

Jan 1, 1954

By C. G. Albert

The clay particles of 2 microns or less required for modern paper coating are predominantly flat plates, lying smoothly on the sheet and producing a high gloss. Operating speeds of today&apos;s coating machines necessitate a clay composition of 60 and sometimes 70 pct solids as against the 35 to 40 pct required in the past. Since clays in suspension may solidify in flow, only those of intrinsically low viscosity can be used as high coating solids. THE literature of paper technology contains a number of articles having reference to developments in the field of coating and filler clays for use in paper manufacture. Much of this information has not been included in mining publications and has therefore not been readily available to all in the mineral industry. Recent developments in this field, including spray drying of clays, are presented here. U. S. Bureau of Mines figures for 1952 indicate that the paper industry consumes more than 50 pct of all kaolin produced and sold in the U. S. As most of the kaolin used by the industry comes from Georgia producers, the fraction of their output destined for paper use is thus appreciably higher than 50 pct. Small wonder that the kaolin industry, especially in Georgia, is highly sensitive to the quality requirements of paper mills and must respond promptly to technological developments in paper manufacturing. The paper industry itself is not the ultimate consumer. For the greater portion of the clay the end product is the printed page, and the demands of printing and publishing have sparked some of the technological advances in paper making which have, in turn, brought about methods employed in the kaolin industry. As compared with the product of 20 or 25 years ago, one of the most striking characteristics of the graphic arts today is the mass production of quality printing of fine pictorial work, much of it in full color. During this time periodicals with printing standards close to those of yesterday&apos;s slick-paper publications that were printed on a slow schedule and for a limited circulation have grown to the point where they go out to many millions of readers, often at weekly intervals. The complexity of technological improvements brought about by this increased circulation is probably not appreciated even by technical people, unless they have had reasonably close contact with the industry. The advance has come about through developments not only in the art of printing, but also in the field of paper making and even at the level of clay mining and processing. The smoothness required for faithful reproduction of the kind of printed matter under consideration is attained with a clay-coated paper. Since the distribution expense of the publication will depend to a great extent on its weight, the paper used must not be too heavy. This means a lower basis weight than was normal for conventional clay-coated papers some 25 years ago. And for this mass production market it becomes necessary to provide a paper having these and all the other required characteristics at a very moderate price—not the premium price conventional clay-coated papers formerly demanded. This challenge has been met by a new method of producing coated paper. In the past, application of clay coating to paper was a conversion operation, performed separately from the making of the base sheet. The newer development is called machine coating. Here application of the coating is an integral step in a continuous process by which wood pulp, clay, and other ingredients are manufactured into a sheet of coated paper. Many more problems are involved in this procedural change than are apparent at a casual glance. The coating operation, for example, must function at much higher linear speed than could be obtained with coating mechanisms previously employed. The application machinery developed to meet this requirement necessitated changes in composition of the coating color.* This created new requirements, summarized below, for the clay employed as coating pigment. In addition to smoothness, a relatively glossy printing surface is needed, and to a large measure it is the function of the coating clay to make possible the development of both these surface characteristics. Traditionally, pigments such as satin-white, prepared by reacting lime with paper-makers&apos; alum, were used to assist in producing a high finish. However, economic considerations and others preclude large-scale use of such material in the new processes. In the 1930&apos;s Maloney&apos; discovered that a certain particle size fraction of kaolin, consisting

Jan 1, 1956

By A. Phillips, D. H. Killpatrick, V. Kerlins

The tensile failure of two dispersion-strengthened Ni-20 Cr alloys was studied and compared to the fracture of a similar alloy with no dispersoid. The fracture characteristics were studied using electron fruc-tography and transmission electron microscopy. In all three cases, the mode of failure was found to be microvoid coalescence. The failure in the dispersion-strengthened alloys was found to have initiated at the particles. The size of the dimples in the fracto-graphs was found to be related to the spacing of the particles, but not to the total elongation before failure. The elongation before failure was found to be related only to the amount of dispersed phase. These results are compared to those predicted by a theoretical model of ductile failure. THE continually increasing strength requirements for creep-resistant materials capable of long life at service temperatures above 1600"F (875"C) have developed considerable interest in dispersion-strengthened nickel-base alloys. The high yield strength of these alloys results from the presence of a dispersion of fine particles of thoria which act to impede the normal motion of dislocations. Many theories have been presented to explain the role of the dispersion in the strengthening of these alloys. A good review of these theories is presented by Ansell.&apos; The ultimate strength of such alloys is not only related to mechanisms raising the yield strength, but also to the amount of work-hardening which occurs. This work-hardening is determined by the work-hardening rate and the amount of plastic strain before failure. Since fracture limits the amount of plastic strain, a study was undertaken to gain a better understanding of the fracture mechanisms in these alloys. Electron fractography and transmission electron microscopy were used to study the fracture characteristics in two dispersion-strengthened alloys and one similar alloy containing no dispersoid. These results are related to the tensile properties of the dispersion-strengthened alloys at room temperature and at 2000°F (1095°C). The results are also related to a theory for ductile fracture. 1) PROCEDURE Standard tensile specimens were made from 0.020-in. (0.051-cm) sheets of three different Ni-Cr alloys. The alloys had nominal compositions of Ni-20Cr, Ni-20Cr-2Th0,, and Ni-2OCr-4Th0,. All alloys were supplied in an annealed condition. The specimens were fractured in tension at room temperature to determine the effect of the dispersed thoria on the fracture appearance. The tensile properties were determined from the average of a minimum of three ten- sile specimens for each condition tested. The fracture surface of all of the alloys was examined by electron microscopy using standard two-stage plastic-carbon replica techniques. Thin foils of the dispersion-strengthened alloys were used to investigate the size and spacings of the dispersion particles, and to investigate sections of the 2 pct thoria alloy taken from areas of the specimen adjacent to the fracture surface. The thin foils were mechanically ground to 0.010 in. (0.025 cm) and then chemically polished to approximately 0.001 in. (0.003 cm) in a solution of 29 g of ferric chloride and 10 ml hydrochloric acid in a liter of water. The polishing solution was maintained at 150"F (65°C) during the thinning operation. The final thinning of the foil was done electrolytically using a solution of 700 ml ethanol, 100 ml 2-butoxy eth-anol, 120 ml distilled water, and 78 ml perchloric acid (70 pct). The potential was maintained at 15 v and the bath temperature at -20°~ (-29°C) during the thinning operation. The final thickness of the foil was approximately l000A as determined from the width of twins boundaries observed in many of the foils. 2) RESULTS AND DISCUSSION The electron fractographs of the fracture surfaces of the alloys are shown in Figs. 1, 2, and 3. The normal interpretation of this type of fractographz is that, as a result of the difference between elastic and plastic properties of the matrix and the particles or other inhomogeneities in the alloy, microvoids are formed

Jan 1, 1969