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By P. M. Aziz, I. Markson, C. S. Barrett

The abnormal after-effect in twisted wires that occurs when untwisting is interrupted by etching con be brought under control and used to study the mechanical properties of thin surface films and how they are effected by reagents and heat treatment. Results are given of studies of oxide films on high purity aluminum. IF a wire is subjected to plastic deformation by torsion and then released, it untwists in the normal after-effect, but under certain circumstances the untwisting is abruptly lessened or reversed by the application of an etchant to the wire.1,2 This abnormal after-effect may occur, for example, if there is a coherent oxide film on the surface of the wire which is removed by the etchant. Following a suggestion of A. H. Cottrell that predicted this effect, it is attributed to dislocations that had piled up beneath the oxide layer and represents the rapid release of residual stresses caused by these dislocations. When the layer is removed, the stress relief may be by escape of piled-up dislocations from the metal, or by an activation of latent sources of dislocations located at the surface, together with rebalancing of elastic stresses to compensate for the loss of stressed material, as in a residual stress analysis determination, these mechanisms acting singly or in combination.' The slower the attack of the reagent, the more gradual is the stress relief and the smaller the change in strain rate when the reagent is applied. A study has been made of the factors that influence the magnitude of the normal and abnormal after-effects with the object of developing techniques suitable for a quantitative investigation of the influence of various surface films on dislocations in wires, and of the rate and extent of the attack on the films by different reagents. It was found that reasonable sensitivity and reproducibility could be achieved if a suitable choice of variables was made and if these variables were held constant through a series of experiments. The method was then applied to a study of oxide films produced and treated in different ways on the surface of high purity aluminum wires, and to a study of the damage to these films caused by various reagents. Experimental Procedure The material used throughout this work was prepared from 99.9968 pct Al. This high purity aluminum was melted, cast into 1/2 in. diameter ingots, and then swaged and drawn without intermediate annealing to 0.040 in. diameter wire. A sketch of the apparatus employed for twisting is shown in Fig. 1. The test wires were mounted into the apparatus by cementing one end of the wire to the beaker and the other to the tube with laboratory wax of high melting point. The length of the wire between the waxed joints was 4.2 & 0.2 cm. Extreme care was taken during mounting to avoid cold-working the wire. The wire was twisted through 335" in 2 to 4 sec by rotating the pinion on the gear box until the vertical post on the rotating table, which was initially touching the horizontal stop, was arrested by the stop. All the tests were conducted with apparatus and reagents at the same temperature (about 25°C). In all tests, except those where the duration of the initial torque was investigated, the torque was applied for a period of 2 min. At the end of this time the table was rotated back a few degrees away from contact with the stop and the wire allowed to untwist. The after-effects were measured by reflecting a beam of light from the mirror shown on the apparatus. After the wire had untwisted for 6 min, a reagent was carefully poured into the beaker and thereby applied to the surface of the wire.. In some tests the liquid in the beaker was removed after a few minutes and replaced by an-

Jan 1, 1954

By Robert G. Nisle

In conducting a pressure build-up test on an oil well, it is often necessary to shut-in the well for a short time prior to initiation of the test. The effect of such a short tern shut-in on the resulting pressure build-up curve is derived. The derivation is based on the Kelvin point-source solution and is a straight forward extension of the fundarnental theory. The magnitude of the effect is evaluatecl and illustrated by an example. It is shown that if the production subsequent to the short term shut-in is at least 10 times the duration of the shrct-in, the effect will he less than 10 per cent. INTRODUCTION It often happens that before a pressure build-up test can be made an additional valve must be mounted on the wellhead, or on arrival at the well, it might be learned that the well had been shut-in several hours the previous day because of a shortage of tankage. In such cases the question is How will such an interruption of production affect the results of a pressure buildup test This work explains how to take account of such a short term shut-in in order that the test can proceed without further delay. The solution presented here makes use of the Kelvin point-source solution used by Horne1 in his treatment of the pressure build-up in wells. Use is also made of the super-position theorem. MATHEMATICAL DERIVATION The well is assumed to have been in production at a constant rate for a relatively long time (several days or more). It is then shut-in for a short time, after which it is again placed in production at the previous constant rate. It continues to produce at this rate until shut-in for a pressure build-up test. The Kelvin point-source solution is expressed by Eq. 1. The sequence of production rates is listed in Table I. TABLE 1 — SEQUENCE OF PRODUCTION RATES Time interval Production Rate At time AT the pressure will be the resultant of the sequence of production rates shown in Table 1. An expression for the super-posed effects may be derived from this table. (Effect of + q for T + ? T) + (Effect of - q for T + ?T-t,) + (Effect of + q for T + ? T - t,) + (Effect of - q for ? T) = Resultant........(2) The desired result is obtained by substituting the effect defined by Eq. 1 for the terms in Eq. 2. The result is Eq. 3. When the logarithmic approximation is made for the exponential integrals and the terms collected the result is Eq. 4. Let T — t2 = T = flowing time following short term shut-in t2 — t1 = 6 = duration of short term shut-in Then T - t1 = r + 6 Substitution of these quantities in Eq. 4 gives p(rw ?T) = P,, -When d<<t - AT then d—&apos;-, T— approaches 1. r + AT In this case the effect of the short term shut-in may be ignored. In order to get some idea of the numerical magnitudes involved take the worst possible case, when AT = 0, that is at shut-in. If the error is made less than some maximum acceptable value at this time, it will be less than the maximum for all subsequent times. d + r Let the difference between the value of y-— and 1 be less than 0.1. Then —6+r — 1 < 0.1 S < O.l T Therefore, if the flowing time following a short term shut-in is at least 10 times the duration of the short term shut-in, the error introduced by ignoring the short term shut-in will not exceed 10 per cent of T+AT A T

Jan 1, 1957

By Robert A. Jankowski, Charles D. Taylor

The objective of this program was to conduct dust surveys at six longwall sections having double-drum shearers, that were regularly in compliance, and to identify the dust control techniques that were the most effective. As each of the mines selected had a record of regular compliance with the Federal Dust Standard, all sampling was "short-term" (often less than 30 minutes) and no attempt was made to relate the survey results to dust-sampling results obtained by the companies for compliance purposes. The sampling procedures (1) used during this survey were developed jointly by the Bureau of Mines and Foster-Miller Associates, Inc. In addition to monitoring dust levels, measurements were also taken throughout the shift to monitor airflow along the face and water usage on the shearer. This program was a cooperative effort of the Bureau of Mines and the Mine Safety and Health Administration (MSHA). The following MSHA health specialists contributed to its successful completion: Paul Lenyo, CMS&H, Dist. 2; Ellis Mitchell, CMS&H, Dist. 3; Carl Jenkins, CMS&H, Dist. 4; David Stritzel, CMS&H, Dist. 8; and John Prelc, CMS&H, Dist. 9. RESULTS CUTTING SEQUENCE - WORK LOCATION At all mines surveyed, an important factor in controlling dust exposure at the shearer is the design of the cutting sequence so as to allow the shearer operator to work most of the time on the intake-air side of the lead drum. It is generally accepted that most of the dust generated by a double-drum shearer comes from the lead drum, which in the raised position normally takes a full sump. Because the position of the drum that is in the raised position determines the horizon control, the operator must be close enough to carefully monitor its operation. Therefore, his position relative to the lead drum has a significant effect on his dust exposure. Dust profiles, such as those constructed from data collected at Mines A and B (Figure 1), show the large gradient in dust concentrations that can exist between the intake and return air side of the lead drum. When the primary cut is taken head to tail, the lead drum is downwind and dust levels can be maintained at a low level until air has passed the shearer (Mine A). Thus, shearer operators can stay in relatively uncontaminated air. When the primary cut is taken tail to head, the lead drum is upwind of the shearer controls, resulting in higher dust concentrations at the shearer operator&apos;s work location (Mine B). At the mines where this cutting sequence was used, it was company policy for the shearer operators to walk on the intake side of the lead drum, returning to the controls only to adjust the height of the lead drum. DIRECTED WATER SPRAYS AND PASSIVE BARRIERS It is not always possible to keep the shearer operator on the intake air side of the lead drum. Various techniques have been tried to keep the dust generated by the shearer away from the machine operators when they work adjacent to the shearer. At all mines visited, the external water spray nozzles were directed so that dust from the shearer was directed downwind and toward the face, and away from the shearer operators. The effectiveness of using external water sprays to keep dusty air close to the face was noted during Bureau of Mines efforts to develop improved water spray systems (2). Laboratory and underground tests showed that water sprays located properly and directed downwind can create aiflow patterns that move dust generated by the shearer toward the face and away from the shearer operators. Sprays directed upwind, into the airflow, can actually move dust away from the face

Jan 1, 1982

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.&apos; This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,&apos; a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors&apos; paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.&apos;&apos; The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors&apos; 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)&apos; D = 3.55 x 10"3 exp (-5550/)&apos; D = 4.3 x 10"3 exp (-5620/1&apos;)&apos; Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By C. R. McEwen

This paper presents a technique for calculating the original amount of hydrocarbon in place in a petroleum reservoir, and for determining the constants characterizing the aquifer performance, based on pressure-production data. A method for doing this based on a least-squares line-fitting computationwus proposed by vanEverdingen,Timmerman andMcMahon in 1953. We found that their method would not work when there is error in the reservoir pressure data — even moderate error. The technique presented here appears to give reasonable answers when pressure data are uncertain to the degree expected in reservoir pressure determinations. The major change introduced in the present analysis is to limit the least-squares line-fitting to yield only one constant— the amount of hydrocarbon in place. The water-influx constant is then taken as proportional to the oil (or gas) in place. The constant of proportionality can be computed from estimates of effective compressibility and reservoir water saturation. It is also pointed out that the commonly used least-squares analysis assumes all of the uncertainty to be in the dependent variable. The material balance should be arranged so that this condition is fulfilled if correct inferences are to be made from statistical calculations. Examples are shown of the application of the new technique to gas reservoirs—both hypothetical and real—and to the oil-reservoir example of van Ever-dingen, Timmerman and McMahon. INTRODUCTION The amount of hydrocarbon originally in place in a petroleum resenroir can be estimated by means of the material-balance calculation. Simultaneous observations of pressure and amounts of produced fluids are required, together with the PVT data applicable to the reservoir fluids. If water encroachment is occurring, it is desirable to try to infer the behavior of the aquifer, as well as the original hydrocarbon in place, from the pressure-production data. This imposes additional demands on the method of calculation, and uncertainty in the data can result in large uncertainty in the answer. In addition, if the size of a gas cap is to be established, the whole problem becomes indeterminate, as pointed out by Woods and Muskat.1 Brownscombe and Collins2 simulated a gas reservoir and its aquifer on a reservoir analyzer and derived quantitative information on the effect of uncertainty in pressure and aquifer permeability on computed gas in place. Among the various techniques of estimating the performance of an aquifer, the method of van Ever-dingen and Hurst? based on compressible flow theory, seems to have been the most generally successful (see Ref. 4, for example). In this paper we shall confine ourselves to their representation of the aquifer. In 1953,&apos; van Everdingen, Timmerman and McMahon5 introduced a statistical technique for deriving the amount of oil originally in place and the parameters which describe the aquifer. (We shall refer to this technique as the "VTM method&apos;&apos;, as suggested by Mueller.6) Their example reservoir had no gas cap. It has been our experience that the VTM method gives a reasonable answer when the data are very accurate, but that inaccuracy (particularly in pressure) can cause the method to break down. The effect was first observed in gas reservoirs, but has since been seen in oil reservoirs also. In this paper we present another statistical method which has been successful in achieving a reasonable answer where the VTM method has failed. In the new method, one less parameter is derived from material-balance computations. It is assumed that values can be established for effective compressibility in the aquifer and reservoir water saturation independently of the material-balance calculation. The water-influx constant can then be obtained from these data and the quantity of hydrocarbon in place.

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer&apos;s organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.&apos; Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.&apos; Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.&apos; The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By Pablo Hadzeriga

Great Salt Lake brine was subjected, in laboratory scale, to conditions simulating solar evaporation. Solid phases and the variation in composition of the liquid phase throughout the potassium salts crystallization zone are presented. These experimental results are discussed and compare with stable equilibrium data of the quinary system Cl-, SO4, Na+, K+, Mg + + and H2O. The Great Salt Lake brine in Utah is a vast reserve of several potential chemicals which has attracted much attention in the recent past. From the standpoint of an ore reserve, it may be said that the lake contains a low grade ore which has to be concentrated by evaporation of water. Because of the fairly favorable weather conditions in the Great Salt Lake area, it seems reasonable to consider solar evaporation as an economical means of concentration. From the view of phase chemistry, the main constituents of Great Salt Lake brine make it belong to the five component system: C1-, SO4=, Na+, K+, Mg++ and H2O. Because of their low concentration, the presence of other elements may be regarded as having little effect on the equilibrium of the five main components. Equilibrium data for the quinary system of our interest has been available for many years. Using these data, it is possible to calculate how the brine of the lake will concentrate when subjected to solar evaporation. In practicing solar evaporation, the weather factor and supersaturation conditions cannot be ignored, but their introduction into calculations using equilibrium diagrams is almost an impossible task. With the experimental work presented in this paper, an attempt is made to compare the stable equilibrium data of the quinary system as applied to the case of the Great Salt Lake brine and the dynamic equilibrium when that brine is subjected to continuous solar evaporation. Sea water brine belongs to this quinary system when only the major constituents are considered. The study of this system has been carried on since the last decades of the nineteenth century. The reason for these intensive studies was to give a geological explanation to the underground potash deposits. AS a result, many theories were presented trying to relate the equilibrium data with the geological formation, paragenesis and metamorphism of these deposits. Two main approaches were followed for the equilibrium studies of this quinary system. One of them, and the best known to us, was the school started in Germany in the last century by J. H. Van&apos;t Hoff. The other one, which started about the same time, was the school of N. S. Kurnakov in Russia. Both approaches were different and as a consequence generated opposite theories about the geological formation of potash deposits. The Van&apos;t Hoff school studied the quinary system of sea water under careful laboratory control, resulting in stable phase diagrams. During these studies, Van&apos;t Hoff recognized the difficulties in crystallizing some double salts.&apos; ". . . . we unexpectedly found that some compounds whose formation in the solutions under investigation was possible at 25°C, nevertheless totally failed to put in an appearance. These, not to mention the calcium salts, were leonite, MgSO4 . K2SO4 4 H2O; kainite, KC1-MgSO4 . 3 H2O; and kieserite, MgSO4 .H2O. Even exceedingly slow crystallization with the addition of the compounds themselves did not remove the condition of supersaturation in the case of these bodies." However, those salts (leonite, kainite, and kieserite) were included in the stable phase diagram at 25°C as shown in Fig. 1 using D&apos;Ans data.3 The figure also shows the sequence of crystallization of the Great Salt Lake brine according to the stable diagram. In later studies by the Van&apos;t Hoff school, especially by D&apos;Ans,3 Karsten,4 Autenrieth,5,6 attention

Jan 1, 1968

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author&apos;s Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A&apos;) but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968

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&apos;mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK&apos;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. O. Brown

A laboratory investigation was conducted to determine quantitatively the extent to which connate water was contacted and displaced by invading flood water. In these experiments the connate water in unconsoli-dated sand packed columns was completely displaced by injecting water. The nature of this displacement was similar to that previously described for single-phase miscible fluid displacement studies, and thus the presence of a non-wetting immiscible phase did not appreciably change the nature of the displacement. The effects of water injection rate, column length, and oil viscosity on connate water displacement were investi-gated. It is concluded that the connate water in a reservoir is the water which actually displaces oil from the pores of the rock during a water flood. During a water flood the connate water forms a zone which separates the invading flood water from the continuous oil phase. The size and shape of connate water bank is chiefly dependent oil the oil viscosity and the column length. INTRODUCTION Water flooding is one of the most widely used techniques for the secondary recovery of oil. Presently, however, it is still not possible to recover all the oil in a reservoir by water flooding. The research described in this paper was conducted as part of a study to determine the conditions under which 100 per cent oil recovery could be attained by water flooding. The particular objective of this work was to determine if any chemical agent, regardless of its nature, placed in the flood water could be effective in influencing the mechanism of displacement of the oil by water. It has been known for many years that water does not displace all the oil in a reservoir because a portion of the oil is "trapped" and held immobile by capillary forces. This oil is trapped within the pores of a water-wet rock when it becomes broken into discontinuous globules. Initially, when oil is present at high saturations within the pores of a water-wet rock, the connate water forms rings around the points of contact of the sand grains and may even completely fill small cavities between grains, whereas the oil occupies the larger void spaces between the grains.&apos; Under these conditions, the oil in these spaces is in the form of irregular but continuous filaments, the diameters of which depend on the geometry of the sand pores. The filaments are formed by the oil contained in the small cells which are formed between the sand grains and are connected to their neighboring cells by channels or tunnels formed by pendular rings of water. At a high oil saturation, the oil filaments conform approximately to the shape and size of the cells and their connecting tunnels. Starting with this distribution, as the water saturation is increased the water layers in the small cavities and on the surface of the grains grow. As this occurs, the water rings grow and the diameters of the oil filaments decrease. When an oil filament is reduced to a critically small diameter, the filament breaks, and its tunnel fills completely with water. Any oil which remains within a cell after all its connecting tunnels have been water-filled is trapped as a discontinuous globule. Once the oil has become trapped, the capillary forces oppose distortion of the globules and may prevent their being squeezed through the water-filled tunnels. Only a very small pressure gradient is sufficient to keep oil moving as a continuous filament. On the other hand, once the filament has broken into discontinuous oil droplets a relatively large force is required to distort the surface of a drop and move it through a water-

Jan 1, 1958

By M. R. J. Wyllie, H. W. Patnode

In the quantitative interpretation of electric log data it is essential to know the formation factor, defined as the ratio of the resistivity of the formation 100 per cent saturated with brine to the resistivity of the brine.&apos; This concept implies that the formation factor for any given rock is constant irrespective of the resistivity of the brine or solution with which it is saturated. It is apparent that this can be true only when the rock matrix is wholly non-conductive. As reservoir rocks may contain clay or shale having an appreciable conductance one may expect these constituents to influence the determination of true formation factor. The formation factor may be theoretically derived from log data by dividing the resistivity of the mud filtrate invaded formation by the resistivity of the mud filtrate. Such a method of calculntion has implicit in it the assumption that the fluids in the invaded formation are wholly replaced by mud filtrate. that the solid matrix is non-conducting, and that the formation factor of the invaded zone is identical with the formation factor of the uninvaded zone. Since the validity of the first two basic assumptions regarding the insulating character of porous matrices and the displacement of the interstitial fluids in porous media do not appear to be fully established, the formation factors of a number of cores and clay slurries have been measured under conditions suitable for verifying the assumptions and the extent of any errors inherent in them. CORE STUDIES Apparatus and Procedure Resistivity measurements were made on short cylindrical permeable cores which had been previously mounted in lucite.2 The cores were clamped by means of insulated bolts between brass plates about 5 cm square and 1 cm in thickness. The plates were provided with a ring seal to prevent leakage between them and the core mount, and had a centrally located orifice so that fluids could be flowed through the mounted core. The brass mounting plates were used as electrodes and any current flow between them necessarily passed only through the constituents of the intervening core. Fluid saturation of the core, and fluid flow through the core, were effected by a centrifugal pump connected to the outflow end of the core, thus providing a differential pressure across the core of approximately one atmosphere. The procedure used was first to evacuate each core by means of the pump and then to saturate the core with an aqueous sodium chloride solution of known resistivity. The resistance of the core was measured and flow of the solution through the core continued for sufficient time to establish a constant resistance reading. After equilibrium had been reached with one solution, another sodium chloride solution of a different resistivity was flowed through the core and the flow continued until a constant resistance reading was again obtained. This procedure was continued until resistance measurements of the core had been made with a series of solutions within a salinity range from 1.0N NaCl to distilled water. The data obtained enabled the apparent formation factor of given porous rocks when saturated with fluids of different resistivity to be computed and also provided information regarding the ability of an invading fluid to displace interstitial water from a core. Results Berea Sandstone — The first core examined was a specimen of Berea sandstone." This core had been cut essentially parallel to the bedding for permeability studies. The core was clamped in the core holder and saturated with 1.0N NaCl solution and the resistance determined. It was subsequently flushed and the resistance measured when saturated in turn with 0.1N, 0.025N, 0.01N, .005N sodium chloride solutions and finally with distilled water. In flushing the core with each

Jan 1, 1950

By W. R. Strickler, P. Hazebroek, M. Prats

The pressure and production behavior of a homogeneous cylindrical reservoir producing a single fluid through a centrally located vertical fracture of limited lateral extent was determined by using mathematical methods to solve the appropriate differential equation. It is assumed that there is no pressure drop within the fracture — that is, that the fracture capacity is infinite. It was found that the production-rate decline of such a reservoir is constant (except for very early times) when the flowing bottom-hole pressure remains constant. The production-rate decline increases as the fracture length increases. Thus, the lateral extent of fractures can be determined from the production-rate declines before and after fracturing or from the decline rate after fracturing when the properties of the formation and fluids are known. The production behavior over most of the productive life of such a fractured reservoir can be represented by an equivalent radial-flow reservoir of equal volume. The effective well radius of this equivalent reservoir is equal to one-fourth the total fracture length (within 7 per cent); the outer radius of this equivalent reservoir is very nearly equal (within 3.5 per cent) to that of the drainage radius of the fractured well. The effective well radius of a reservoir producing at semisteady state is also very nearly equal to one-fourth the total fracture length. It thus appears that the behavior of vertically fractured reservoirs can be interpreted in terms of simple radial-flow reservoirs of large wellbore. INTRODUCTION An earlier report1 has considered the effect of a vertical fracture on a reservoir producing an incompressible fluid. That investigation of the fractured reservoir producing an incompressible fluid was started because of its simplicity. Thus, pertinent behavior of fractured reservoirs was obtained at an early date, while experience was being gained of value in the solution of more complicated fracture problems. One of these more complicated problems, and the one discussed in this report, considers the effect of a compressible fluid (instead of incompressible fluids) on the production behavior of a fractured reservoir. In the incompressible-fluid work mentioned, it was shown that the production rate after fracturing could be described exactly by an effective well radius equal to one-fourth the fracture length whenever the pressure drop in the fracture was negligible. Because of the simplification in interpretation, it is a matter of much interest to determine whether the production behavior of reservoirs producing a compressible liquid could be described in terms of an effective well radius which remains essentially constant over the producing life of the field. The details of the mathematical investigation are given in the Appendixes. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The reservoir has an impermeable circular cylindrical outer boundary of radius re. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below the producing layer (reservoir). It is assumed that there is no pressure drop in the fracture due to fluid flow. Fig. 1 indicates the general three-dimensional geometry of the fractured reservoir just described. When gravity effects are neglected, the flow behavior in the reservoir is independent of the vertical position in the oil sand. Thus, the flow behavior in the fractured reservoir is described by the two-dimensional flow behavior in a horizontal cross-section of the reservoir, such as the one shown in Fig. 2. Production is due to the expan-

By J. O. Brittain, E. Lautenschlager

Yield point measurements were made on polycrys-talline specimens of a iron deformed various amounts at 770, 1950, or 273°K, aged, and redeformed at 77: 195°, or 273°K. When the prestrain temperature is lower than that subsequent to aging, the yield point return is suppressed relative to specimens deformed at the same temperature both before and after aging. The degree of suppression is a function of both the magnitude of prestrain at the lower temperature and the difference between the deformation temperatures before and after aging. It is proposed that the suppression is caused by the formation of dislocation barriers during the initial low-temperature deformation. The aging kinetics of polycrystalline a-iron wires deformed at 77o or 303oK were studied at 44 " and 64 "C using internal friction measurements. No change was noted as a result of the difference in prestrain temperature. IN an earlier investigation1 it was observed that the return of the yield point was suppressed when a poly-crystalline specimen of a iron was plastically deformed at 77oK, aged at room temperature, and subsequently tested at room temperature. In order to investigate this observation, a research program was undertaken to measure the effect of prestrain temperature on the strain aging of a iron.&apos; According to Thomas and Leak,3 return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solution, while the return of the yield point as a function of aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,4 the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point upon restraining. In this experiment, both methods of measuring strain aging were employed in order to have two independent measurements of the strain aging phenomenon. In a previous study,5 the strain aging kinetics of a similar lot of a iron were measured for specimens which were prestrained and tested at the same temperature over the range of 77" to 273°K. Although some differences were found in the correlation of the two methods employed for measuring strain aging, the kinetics of strain aging were unaffected by the change of prestrain and test temperature. In another study,6 dislocation line tension and the density of the solute atmosphere were found to contribute to the return of the yield point when ingot iron specimens were prestrained at 303°K and tested at a lower temperature, namely 77°K. This paper is concerned with changes in strain aging kinetics produced by pre-straining at 77" to 303°K and testing at either the prestrain temperature or at higher temperatures up to 273°K. EXPERIMENTAL PROCEDURE The polycrystalline a iron specimens used in both the tensile and internal friction tests were 0.033-in. diam ingot iron wires, wet hydrogen treated and re-carburized. A more detailed procedure for processing a 3/16 in. ingot iron rod (nominal wt. pet composition: Fe - 0.013; C - 0.0125; Mn - 0.023; Si -0.005; P - 0.0023; S - 0.11; Cu - 0.004 N) to 0.033 in. diam specimens containing approximately 0.020 wt pet C and no detectable nitrogen with a grain diameter of 0.033 to 0.040 mm is given elsewhere.5 Immediately prior to testing, specimens were solution treated for 15 min at 700o ± 2°C in a static vacuum of less than 50 ?. of Hg and rapidly quenched into an ice-water bath while still enclosed in a 3 mm quartz vial. The internal friction specimens had 8-in. gage lengths and the tensile specimens had 2-in. gage lengths. The wires used as tensile specimens were first run as internal

Jan 1, 1962

The authors of T.P. 4179 have conducted a large number of experimental water floods, and the data are reported in a very clear manner. These data show significant variations of residual oil saturation with changes in wettability, interfacial tension, flooding rate, and oil-water viscosity ratio. Furthermore, some of the data obtained cover a range of variables not previously reported in the literature. It is our opinion that at least some of the observed variation in oil recovery can be obtained only in floods made under conditions identical with those used by the authors. There are other systems which may be said to have the same wettability, but which exhibit an entirely different qualitative dependence of oil recovery on the experimental variables. In this regard, we would like to direct attention to several items which we feel are not given sufficient consideration in the paper. The first of these items has to do with wetting equilibrium. A survey of the current literature will reveal that little is known, and even less is understood, about wetting equilibrium. This is particularly true of the relation between contact angle measurements made under static conditions, and the wettability existing under the dynamic conditions of floods carried out at relatively high rates. We feel that this is a very important consideration, particularly in the floods the authors performed under what they consider to be "water-wet" conditions. It is our opinion that wetting equilibrium did not exist in these floods, except possibly at the very lowest rates. This opinion is in part based on some flooding tests we have made which are very similar to some of those described by the authors. These floods were made in unconsolidated cores, 6 in. long and 13/4 in. in diameter, made up of carefully graded glass spheres of the approximate size of the sand grains used in the subject paper. The cores were mounted vertically, and distilled water was used to displace a refined oil equivalent to the authors Soltrol C. The glass spheres had previously been carefully cleaned so that they were strongly wet by the water. The floods were made with and without an interstitial water saturation. When interstitial water was present, the solid surfaces were mostly covered with water prior to injecting the flooding phase. Consequently, a condition very near wetting equilibrium existed throughout the flood. The data in Fig. A show that under these eircumstances, rate had no influence on residual oil at flood-out, over the range of rates studied. On the other hand, in the absence of interstitial water, the surfaces are all covered with oil before the displacement. To achieve wetting equilibrium the injected water must displace the oil from the surfaces themselves. This is not a fast process. Therefore, the effective dynamic wetting condition in floods of this type must depend upon the flooding rate. When the flood rate is very low, compared to the rate at which wetting equilibrium is attained, the residual oil saturation at flood-out is essentially the same as the residual obtained when interstitial water is present. This is shown in Fig. A, and occurs because the dynamic wetting conditions are the same in both cases. However, at moderately high flooding rates, the rate has an important bearing on the amount of oil recovered because in this case the attainment of surface equilibrium is the slow step. We believe that, in the absence of an interstitial water saturation, oil recovery varies with rate because of the reasonably slow approach to wetting equilibrium which occurs during the displacement. In fact, as the rate is increased, the oil recovery performance indicates the core is becoming progressively less water-wet. At the highest rate there is even considerable simultaneous production of oil and water after breakthrough. This does not occur at the lower flooding rates, nor is there appreciable simultaneous oil and water produc-

Jan 1, 1957

By J. C. Deppe

A method is presented for calculating approximate injection rates in secondary recovery operations. The method can be applied to cases of unequal fluid mobilities, irregular well patterns and boundary patterns. The steady-state pressure distributions for the four flood patterns reported by Muskat and for five additional patterns reveal that most of the difference in pressure between the injection and producing wells occurs in regions around the wells which can adequately be described as regions of radial flow. This leads to a method of calculating injectivity by approximating the flood pattern with radial flow elements (or a combination of radial- and linear-flow elements for some patterns such as the direct line drive). Irregular and boundary patterns can also be approximated by radial and linear elements. Each of these elements can be described by radial-and linear-flow equations and the results combined as series flow resistances to give an approximate equation for the initial injection rate. The mobility ratio does not affect the initial rate; therefore, if the well pattern is one of those regular patterns for which theoretical rate equations have been derived for unity mobility ratio, the approximate initial rate equation can be improved by adjusting it to match the theoretical equation. The available theoretical rate equations are listed, including five new cases. As the flood progresses, the injectivity changes because in general the flood front will divide the pattern into areas of different fluid mobilities. Simple shapes can be assumed for the flood front so that both areas can be divided into radial- and linear-flow elements. Radial- and linear-flow equations are applied to these elements to account for the change in flow resistance behind the front. To calculate injection rates after breakthrough, it is necessary to know the sweep efficiency at breakthrough. Areal sweep data are available in the literature for a number of patterns, and sufficiently accurate breakthrough sweep efficiency can be estimated from these data if it is not otherwise available. Again, simple shapes for the flood front can be assumed after breakthrough, and injection rates can be calculated for the remainder of the flood. When areal sweep data are available, these data can be used to cbeck. the calculated injection rates after breakthrough. Injection rates calculated by this approximate method compare favorably with available model data. INTRODUCTION When the fluid mobilities in the swept and un swept regions are equal, the injectivity will not change as the flood front advances; and for regular patterns it can be calculated by mathematical formu1as.l When the fluid mobilities in the swept and unswept regions are not equal, the injectivity will increase or decrease as the flood front advances. In this case, the injectivity has not been calculated by analytical means for any practical well pattern; and, furthermore, scale model and analog4,6 results have been published only for the five-spot pattern. The main object of this paper is to present an approximace method for calculating injectivity for the case of unequal mobilities. The method can be applied to regular, irregular and boundary patterns. Before the approximate method is discussed, the analytical formulas for equal mobilities will be summarized, and the analytical solution for radial flow with unequal mobilities will be used to show how the injectivity changes as the flood progresses. EQUAL MOBILITIES, REGULAR PATTERNS In a flooding operation the injectivity, the rate at which fluid can be injected per unit difference in pressure between injection and producing wells, depends on basic physical properties and, in addition, on three variables to be treated here—the area of the swept region, the fluid mobilities in the swept and unswept regions, and the well geometry (pattern,

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG&apos;s ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid&apos; have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey&apos; presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By S. R. B. Cooke, H. S. Choi, D. H. Harraway, I. Iwasaki

The mineralogy of natural iron ore samples and their slimes have been investigated and the nature of slime interference in iron ore flotation has been studied. The results have been correlated with the flotation behavior of a natural ore sample. Various conclusions have been reached as a result of these studies. In the flotation of iron oxide ores, desliming is generally considered to be an essential step to successful separation, irrespective of whether the iron oxide or siliceous gangue minerals are to be floated, although some workers have found empirically that certain collectors and reagent combinations are less sensitive to the presence of slime than others. The detrimental effect of slime is considered to be twofold. First, the presence of slime presupposes a high reagent consumption because of high specific surface. When clays are present and when cationic collectors are used abstraction by ionic exchange may augment this condition. Attempts to compensate by the addition of large amounts of reagent result in only partial correction. Second, slime coatings on granular particles tend to interfere with the bubble-mineral contact. The nature of slime coatings in flotation is quite complex and has been the subject of considerable study; an attempt was recently made by Fuerstenau et al.&apos; to relate the slime-coating density with flotation recovery and with the properties of the electrical double layer at the mineral surfaces. Although major constituent minerals in the oxidized iron ores of the Mesabi and Cuyuna ranges are hematite and goethite (limonite) as the iron oxides, and quartz and chert as the siliceous gangue, very little is known of the mineralogy and of the chemical and physical characteristics of the slimes, and still less of the interaction between slimes, collector, and the mineral surfaces. For pragmatic reasons iron ore slimes are defined as — 20p material, based upon the calculated settling velocity of a quartz sphere of the stated diameter, and of all other equal-settling mineral particles. Active slime interference with flotation is usually attributed to particles 5p in size or finer, the extent of such interference appearing to depend not only on the mineralogy but also on the size distribution of each mineral in the slime fraction. The objective of this work was to acquire a more specific knowledge of the constitution of iron ore slimes and of their role in flotation. The mineralogi-cal composition of natural slimes was obtained by differential thernal analysis (hereinafter referred to as DTA), electron microscopy, and chemical and X-ray analyses. Some flotation tests were made on natural ore samples. The surface properties of several constituent minerals were investigated by electrophoretic measurements and by determination of the adsorption of some typical flotation collectors. Finally, simplified flotation tests were made on granular goethite and quartz in the presence of various artifically prepared slimes; the results were compared with laboratory flotation tests made on natural ores. MATERIAL AND METHODS Mineralogy of Some Iron Ore Slimes: Samples of two wash-ore tailing::, hereinafter identified as A* and B, *Sample A of the present investigation 18 the same am ore A in ref. 3. of a wash ore C, and of a paint rock D, all from the Mesabi range, were selected for investigation on the basis of prior information concerning their flotation behavior. The two wash-ore tailings, when deslimed, were known to respond well to flotation, whereas the wash ore was high in goethite, tended to be slimy, and responded poorly to flotation. The paint rock also exhibited sliming tendencies, and was suspected to contain relatively large quantities of clay minerals because of its high A1203 content. Gruner states that the paint rock of the Mesabi frequently contains kaolinite. To ascertain the relative sliming tendencies of each sample a standardized desliming method was employed. All samples were ground through 65 mesh using jaw and rolls crushers. A 500-g sample of each

Jan 1, 1962