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By W. A. Hockings, D. W. Fuerstenau, A. L. Mular

This paper briefly describes a simple air pycno-meter and its use for rapid determination of the composition of mixtures of solid particles. Research on such problems as the pelletizing of solids, the mixing of solid particles, and the comminution of mixtures can be simplified by means of this analytical tool. THEORY OF OPERATION Liquid pycnometers1 are commonly employed to measure volumes. These devices are time consuming and sometimes give inconsistent results. The liquid used in the pycnometer may have an undesired influence on the material to be measured; moreover, complete displacement of air by the liquid is seldom

Jan 1, 1963

By John J. McKetta. Jr., Louis B. Lesem, George H. Fancher

The proration of oil produced in the field frequently is based partially or entirely upon the gas-oil ratio of wells. The measurement of the gas-oil ratio is one of the more important field tests in regulatory and pro-ration work, and the test always should be conducted according to standardized methods and procedure. Obviously, the gas-oil ratio and the volume of gas produced by a well depend upon many factors but should be independent of the method of measurement and of the devices used to measure gas and oil. Consequently, the volume of gas accompanying a barrel of oil produced by a well may be measured by any reliable and accurate device or instrument. Frequently either a critical flow prover or an orifice well tester is used for this purpose, and for a particular well the same rate of flow of gas should be obtained regardless of whether a critical flow prover or an orifice well tester is employed in the test. In Texas, when using either instrument, either Capacity Table 1 or 5' is employed in making the necessary computations. If the tables are used, a discrepancy always is found whenever the two instruments are compared by extrapolation to the same conditions of flow. Clearly, Tables 1 and 5 must be at fault in some respects. The orifice well tester and the Bureau of Mines type of critical flow prover are essentially the same instrument; both devices utilize a square-edged orifice 1/8 in. in di-ameter as the primary element, and both freely discharge gas to the atmosphere. Tables for the orifice well tester' have been published in the ranges of 0 to 15 in, of water and 0 to 40 in. of mercury (Hg) differential in pressure. Coefficients for the critical flow prover have been published for differentials in pressure greater than 75 psia. An extrapolation of either differs from the other set of data as much as 18 per cent at some points. No immediately obvious reasons for the discrepancy was found, and data available from the literature were insufficient to effect reconciliation. Consequently, a series of experiments was performed to check the available data and to determine discharge coefficients for the two devices in an overlapping range of differential pressure. The correlating equation used in preparation of tables such as Tables 1 and 5' is the so-called hydraulic equation, Q = C1 vh .....(1) The tables cover orifice sizes from 1/8 through 1 1/4 in. A second set of tables, for use with greater differentials in pressure, apply only to the 3/4, 1, and 1 1/4-in. orifice plates over a pressure range of 0 to 40 in. of Hg. The correlating equation used in preparation of the tables is Q = C2 vH(29.32 + 0.3H)/G . (2) Each of these equations is valid only for the range to which it has been applied, and neither equation is valid for extrapolation. Theoretical equations for flow through an orifice are based upon assumptions of fractionless flow and an emergent jet the size of the orifice. A multiplier, C,, called the discharge coefficient, is inserted into the theoretical expression to compensate for both frictional losses and the contraction of the jet experienced in the plane of the orifice. Buckingham3 shows that C, should vary with the ratio of upstream to downstream pressure for flow of a compressible fluid at any average linear velocity through the orifice less than the velocity of sound. Work published by the National Advisory Committee for Aeronautics4 indicates that the variation continues into the so-called critical flow region until the vena contracta coincides with the plane of the orifice. The NACA work, however, does not indicate a leveling off of the coefficient. The work of the Bureau of Mines5 for the critical flow prover was based on differential pressures greater than 75 psi and indicates that the discharge coefficient, Cd, is constant in this region at a value of about 0.86.

Jan 1, 1958

By C. R. Fast

In order to evaluate the ability of a Hydrafrac treatment to effect a sustained increase in well production, data were accumulated on the first 65 wells in 26 fields treated by Stano-lind. Since these data were obtained from such a large number of fields, it is felt that individual well or reservoir characteristics do not affect the overall picture, as might be the case if the study were made in one field or one group of wells in a field. These data are tabulated in Table I and plotted on Figs. 1 and 2. An analysis of Fig. 1 shows that at the end of six months, 75 per cent, or 45, of 60 wells on which data were available showed a sustained production increase. At the end of two years, data were available on 25 wells. Of these, 15 wells, or 60 per cent, showed a sustained production increase. At the end of three years, 55 per cent, or 10, of 18 wells had a production rate greater at that time than before Hydrafrac treatment. The lack of information on additional wells at the end of the third year is primarily a result of the small number of treatments conducted in the early stages of field application

Jan 1, 1952

By D. W. Fuerstenau, L. M. Berlioz

In 1957, Charles1 first presented an analysis of a relationship between the energy expended in comminution and the extent of size reduction achieved. Subsequently, Schuhmann extended and interpreted Charles' approach to comminution. According to their analysis, the energy, E, expended in comminuting unit mass of fairly uniformly-sized material is related to the size modulus of the product, k, by where a is the distribution modulus (slope of the log-log cumulative size distribution plot) and C is a constant, which is primarily determined by properties of the solid. If there is any fundamental basis for the E vs k relationship, E must necessarily be concerned with the useful work for the size reduction process and not necessarily the work input, as discussed in detail by Harris.3 Charles and numerous other investigators tested this equation only by relating k to the grinding time, assuming expended energy to be directly proportional to time, but never directly measuring power. In our laboratories, we recently constructed a special batch ball mill with which the power could be accurately determined with torque measuring apparatus.4 With this device, a direct test of the Charles relationship could then be made for ball milling. 5 EXPERIMENTAL A stainless steel mill, 11.5 in. long and 10 in. in inside diam, lined with eight low-silhouette lifter bars, was used for these experiments. The grinding media consisted of 30 kg of single sized, 1-in. diam, stainless steel balls, which occupied about 50% of the total mill volume under static conditions. The void fraction of the static ball load was approximately 0.4, and for the dry grinding conditions used, the corresponding interstitial volume was filled when about 3300 g of the dolomite feed material was present. The 7x9 mesh dolomite used as feed was obtained as a natural, uncrushed product thus as- suring a random distribution of feed particle shapes. Charge weights of 660, 1320, 1980, 2480, 3300, 3960 and 5280 g, which correspond to 20%, 40%, 60%, 80%, l00%, 120%, and 160% of the interstitial load, respectively, were used. Grinding times of 20, 40, 60, 80, 100, 150, 200 and 300 revolutions were considered, with the mill operating at 54 rpm (approximately 60% of critical speed). The tests were made sequentially, in that the size distribution obtained after a certain grinding interval was utilized as the feed for the subsequent period of grinding. Agreement with control experiments where the mill ran continuously for the entire interval was excellent. Torque measurements were made utilizing a Baldwin-Lima-Hamilton SR-4 torque pickup in the manner that has been described previously.3 Standard wet (to obtain the -400 mesh material) and dry sieving procedures were followed using the Tyler full screen series. RESULTS The Gaudin-Schuhmann size distributions obtained in all of these experiments are characterized by distribution moduli (slopes), a, of about 0.66 and are representative of normal dry batch ball milling of a material like dolomite. As an illustration of typical

Jan 1, 1968

By Frederick C. Langenberg

IT has been shown1 that copper can be removed from iron-base alloys by solvent extraction with molten lead and sodium sulfide slags. In these processes copper removal is favored by a positive deviation of copper in iron from ideal behavior. Chou' determined the distribution of copper between liquid silver and iron and obtained a value for the activity coefficient of copper in iron at 1600°C, y°, of 9.12. Chipman" calculated the activity coefficient from the Fe-Cu phase diagram to be 12 at 1600°C. More recent work by Koros and Chipman" yields a value at 1600°C for y V equal to 8.0. In this latter work, the distribution of copper between silver and iron was measured at 1600°C, while the activity of copper in the silver phase was determined from calculations based on the Ag-Cu phase diagram. The present work presents another value of based on calculations from the Cu-Pb phase diagram, on the heat of mixing data for the Cu-Pb system, and on an experimental study of the distribution of copper between iron and lead at 1600°C. These experiments were part of a larger research on the removal of copper from iron-base alloys conducted at The Pennsylvania State University. Experimental Procedure—The distribution of copper between pure iron and lead at 1600°C was made in the furnace assembly shown in Fig. 1. The melts were made in high purity alumina crucibles under an atmosphere of prepurified argon. Temperatures were read with an optical pyrometer sighted into a %-in. hole drilled in the inductor. Extensive calibration of the optical readings with immersion readings had been carried out previously. The initial charges consisted of 100 g of electrolytic iron and varying weights of copper. The melts were brought rapidly to 1600°C and 75 g of lead added. The temperature was quickly readjusted to 1600°C, and the melts were held for 10 min at this temperature. A sample was then drawn from the iron layer in a fused silica tube. This sample was analyzed to determine the copper content of the iron layer at equilibrium, while the copper content of the lead layer was determined from a material balance. The validity of the material balance was confirmed by a chemical analysis of the entire lead layer for one heat in which the crucible was removed and quenched after the iron sample was taken. The calculated copper content of the lead-rich phase was 1.18 pct; while the entire lead layer analyzed 1.20 pct Cu. The distribution results are shown in Fig. 2. The distribution constant, N,.'r'"/N, is equal to 3.95. Discussion—From the Cu-Pb phase diagram' it can be seen that lead-rich liquid Pb-Cu solutions

Jan 1, 1957

By P. A. Toynbee

An experimental air-slide classifier1 has been applied to the de-dusting of ground dolomite in an attempt to produce a grade of -30 +150 mesh (B. S. Sieves) material from a raw material containing 30-35% of the -150 mesh fraction. Air flows varying between 1.5 and 2.5 cu ft/sec sq ft of screen area were used. The throughput of dolomite was between 80 and 100 lbs/h. inch of screen width. The size analyses of the de-dusted material and of the original dolomite are shown in table at right. The proportions of the +100 mesh material in the feed and in the de-dusted products have been used to calculate materials balances, on the assumption that there is no loss, as dust, of this +100 mesh fraction. By interpolation, it can be shown that a de-dusted product recovery of 68.5% will be obtained at an air flow of 2.13 cu ft/sec sq ft of screen area. The feed material contains 68.5% of +150 mesh material, so that if the de-dusting gave a perfectly sharp cut, the product would contain no material less than 150 mesh. Further calculations based on the size analyses, show that, at an air flow of 2.13 cu ft/sec sq ft of screen air, the -150 mesh fraction in the de-dusted product will fall just below the specified maximum limit of 5%.

Jan 1, 1964

By A. G. Metcalfe

THE failure to detect any change in the thermal properties of cobalt at the Curie point would appear to indicate that the apparatus may have a limited sensitivity. The Curie temperature has been determined by direct methods to be 1121+3°CP and 1131°C.3 The specific heat has been determined many times'.' and weighted values are given in Table I. The allotropic transformations in iron and titanium, used by the authors to test the experiment method, involved a volume change of the order of 3 pct on going from the close-packed to the body-centered-cubic lattice. These energy changes are likely to be much larger than those involved in a diffusionless transformation from a hexagonal to a cubic-close-packed lattice. However, it has been pointed out that thermal observations are unreliable in the detection of phase changes when these are near a Curie point.' James 0. McCaldin and Pol Duwez (authors' reply)—The sensitivity of the present technique is limited to first-order transformations, so that gradual changes in specific heat, e.g., in the vicinity of Curie points, are not detected. Furthermore, the existence of first-order transformations with latent heats much smaller than those occurring in the known allotropic transformations of iron and titanium is, we agree, still pending.

Jan 1, 1956

By J. O. McCaldin, P. Duwez

ALLOTROPIC transformations between 1000° and 1900°C have recently been reported for several metallic elements. Since the proposed transformations are based on limited evidence, it was decided to examine the elements in question as well as some refractory metals by thermal analysis with a photoelectric technique similar to that described by Hug-gins, Roll, and Udin.1 In this method, a lead sulphide cell was used to detect thermal radiation from an electric-resistance heated strip specimen. A thermocouple spot welded to the specimen was used to calibrate the temperature of the system under steady temperature conditions, and recording was accomplished with a cathode ray oscilloscope. In the method used by the present authors, the temperature calibration was omitted and the cathode ray oscilloscope was replaced by a recording galvanometer. This technique, in which electric current passing through the specimen heats it, will be referred to henceforth as Method 1. Another arrangement was required for those cases where the specimen could not be formed into a wire or strip suitable for resistance heating. In such cases the specimen was a sintered compact heated by thermal radiation from a hot tungsten strip, Fig. 1. The specimen was insulated from the heating strip with a thin layer of thoria powder or suspended on 0.004 in. tungsten wires. The take-up spring had just sufficient tension to prevent buckling of the heating strip due to thermal expansion. This technique will be called Method 2. Both methods were tested with specimens of iron and titanium and the well known allotropic transformations, a toy and ? to 8 in iron and a to in titanium, were very clearly detected. Fig. 2 shows one of the records obtained for titanium. For this particular experiment, the iodide titanium specimen was a square rod 0.080 in. on an edge and 3 in. long.

Jan 1, 1955

By Austin E. Dwight

IT has been shown by Oelsen and Wever' that the effect of a solute element on the allotropic transformation in iron is dependent upon the quantity

Jan 1, 1957

By P. H. Scott, Walter Rose

Recent papers by S. T. Yuster have called attention to the largely ignored concept that there will be a transfer of viscous forces across fluid-fluid interfaces during the flow of immiscible fluid phases through porous media. This leads to the implication that the relative permeability us saturation function, as applied to each of the fluid phases of the system, will in some way be dependent on the viscosities of all the other fluid phases which are contiguous to the flowing fluid of interest. In fact, Yuster has selected and analyzed the properties of a capillary-tube model of the reservoir-prototype flow systems and concludes from his studies that relative permeability values will be very markedly influenced by the viscosity ratio in two-phase systems. On the other hand, relative permeability data have been reported in the literature for more than 20 years; and where these data are consistent at all, they consistently how no dependence on viscosity ratio (cf. chapter 7 of Muskat3 for a resume of past experiniental work). This paradoxical situation has prompted us to re-evaluate Yuster's work. The major flaw we find has to do with the properties of the model Yuster employed to give qualitative support to his predictions. This model is defective in that important surface area parameters characteristic of the prototype-reservoir flow system have not been propertly scaled. Fig. 1 shows how we believe Yuster's model should be modified to circumvent this difficulty. It depicts the capillary tube of radius R and length L, comprised of two elements in series. The first part of length, L has the nonwetting phase flowing centrally out to a radius distance r, where an interfacial boundary exists with the wetting phase which flows in the concentric annular pace of the tube. The second part of length, L-L,. has the

Jan 1, 1953

By C. A. Fothergill

An improved blotter model is described which makes use of a plastic sheet as base for the blotter field and pins to represent the input wells. The model is simple to construct and adapt and is particularly useful for demonstration purposes. Operational details are given. INTRODUCTION The blotter model was first applied to the investigation of oilfield problems by Wyckoff, Botset and Mus-kat,' primarily in order to demonstrate the flood patterns which could be expected from various arrangements of input and output wells in waterflooding projects. In recent years the model has been largely superseded for analog studies by the potentiometric and electric analog models which are more refined and versatile, since they can simulate the form, and, in certain cases, permeability variations which it is not possible to do with the blotter model. However, the latter is still used for analog studies where the reservoir can be represented as being uniform in thickness and permeability, and where a visual record of the flood advance is required. Ramey andNabor,2 for example, have applied the model to the investigation of areal sweeps in oil recovery by in-situ combustion. Because of its limitations, the blotter model can be used in general for only very simple arrangements of input and output wells, but within these limitations it has a definite advantage over all other types, in that it provides a picture of the advancing flood using the simplest and most easily constructed apparatus, by contrast with the gelatin model, for example, which requires more elaborate equipment. Moreover, the experiments can be quickly repeated and modified if necessary, whereas considerable time is required to prepare a gel field, compared with that required for the preparation of sheets of conducting blotting paper. For these reasons the blotter model can be very useful for demonstration and teaching purposes, enabling the student to experiment for himself with different arrangements of input and output wells. A model has been constructed for this purpose which is simple to operate and adapt. The model (Fig. 1) consists of a base platform or box, approximately 12-in. square, on top of which are screwed three lathes of 1/2 -in. square section to form three sides of a square 6 in. in length. This forms the support for a sheet of Cobex, transparent plastic, thickness .003 in., on which is carried the blotting paper representing the field. The plastic is flexible and relatively soft, and can be attached to the support by cellulose tape so that it can be easily removed when required. The input wells are represented by brass drawing pins pressed through the plastic sheet from the underside until the points are just projecting through the top; these are connected in the circuit as shown in Fig. 2. The sheet of blotting paper of required shape and size is saturated with a solution of 0.2 n-potassium sulfate to which has been added a saturated alcohol solution of phenol-phthalein at a strength of 10 cc/liter of stock solution. The surplus water is removed and the blotting paper placed in position on the plastic sheet making contact with the drawing pins and the sheet (which is an insulator). The anode consists of a second sheet of blotting paper cut as shown and saturated with the same solution. This is suspended from a laboratory stand, being connected to the conducting wire by means of a crocodile clip and making contact with the horizontal blotting paper at the projecting point. This is the method used by Ramey and Nabor and which permits the hydroxyl ions or colored front to reach the anode. As shown in Fig. 2, the electrical voltage used is 220-v DC and a shunt is placed across the terminals to step down the voltage as required. Further adjustment can be made as necessary using a lamp board in series with the shunt to obtain the

Jan 1, 1958

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.' The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory' that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"' which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

By F. W. Jessen, John C. Miller

In many areas where carbonate rocks form important parts of the stratigraphic sequence, stratigraphers have experienced varying degrees of difficulty in differentiating and correlating limestone and dolomite units in both surface and subsurface work. With early Paleozoic rocks of the Mid-Continent, insoluble residues yield a remarkable amount of strati-graphic data and relatively good correlations may be carried over broad distances.' Unfortunately, neither such information nor electric logs and radioactive logs have been particularly helpful in interpreting the limestone sections of the Permian Basin of West Texas. This is because: (1) the variations in the sections may be very slight; (2) no completely satisfactory method of interpretation has been developed; and (3) the measurements themselves are not sensitive enough for small variations. Also, such logs are influenced by the fluid content. Paleontology and micro-paleontology remain the ultimate arbiters. As a routine tool, however, paleontol-ogical examination is slow and tedious. Chemical analysis may be used, but this, too, is extremely slow. Although rocks are not classified according to chemical composition, there is considerable variation with rock types. Correlation by chemical composition has two advantages, first, the characteristics determined are subject to minimum human error and interpretation, and secondly, the lithologic changes are not masked by fluid content as in the case of electric and radioactive logs. Some fossils concentrate certain elements which tentatively might be used to date rock units.' Rapid chemical analysis by spec-trographic means could be used as an adjunct to other means employed in correlation work, or might, in itself, present a suitable method. PURPOSE OF THIS INVESTIGATION Sloss and Cooke' have published data concerning spectrographic analysis of limestone rocks specifically for purposes of direct correlation of a single formation. These authors found satisfactory evidence that differences in percentage of four elements (Mg, Fe, Al, and Sr) in the Mississippian limestones of northern Montana were useful in carrying out correlation of this formation over a distance of approximately 50 miles. It was concluded from the preliminary work that the spectrochemical method offered possibilities of solution of some problems of correlation heretofore not possible. Since the work of Sloss and Cooke' was confined to one particular limestone zone, extension of the use of the method to examine two or more geologic formations would aid materially in the over-all problem of correlation of such rocks. Equipment is now available commercially with which very rapid spectrographic analyses may be made, and hence the problem was to determine whether the variations existing in the minor constituents of limestones were sufficient for use in possible correlation. Qualitative and semi-quantitative investigations were made to determine whether significant changes in the chemical condition occurred. It was a further purpose to investigate the geologic time-boundaries to see whether significant chemical variation could be found corresponding to the paleontological breaks. It was desirable to attempt correlation of a thick section of limestone or dolomite rock and to have as much information as possible on the section. Furthermore, it was felt that examination of formations more difficult to correlate by other means would enhance the value of the method should definite points of correlation be found. Samples were chosen from the Chapman-McFarlin Cogdell No. 25 well in the Cogdell field, Kent County, Tex., and from the General Crude Oil Co., Coleman No. 193-2 well in the Salt Creek field, Kent County, Tex. These fields belong to the famous series of "Canyon" reef fields of West Texas. Cores from the above wells were available from the United States Geological Survey, Austin, Tex. THE SPECTROGRAPHIC METHOD The choice of procedure to be followed in this investigation was based on the anticipated requirements peculiar to the problem. Since the problem was primarily to investigate the possibilities of applying the spec-trograph to problems of correlation in thick carbonate sections, a precise quantitative analysis did not appear necessary. A qualitative analysis to show the possible absence of presence of any element, or a semi-quantitative analysis of the elements present to show the relative changes in magnitude of selected elements was required. Both types of analysis were employed. The two most widely applied methods of semi-quantitative estimates are those of Harvey and of Slavin4,5 though various other procedures have been described.6 while the Harvey method has been modified by Addink,7 this refinement did not seem necessary to the present problem. Essentially, the procedure employed is a variation of the total energy method of Slavin with two exceptions: (1) stressing matrix effect, and (2) using densitometer measurements. As measured by a densito-

Jan 1, 1956

By Robert Maddin

crystal prior to, polishing in order to eliminate coring. This treatment may be accomplished by wrapping the single crystal tightly in very thin, dead soft, brass foil and annealing in the presence of air for 20 hr at 800°C. Since the wrapping encircles the sptcimen three to four times, only a very slight amount of oxidation occurs on the specimen surface. On unwrapping one of these cylindrical single crystals. in. in diam by ro in. long (72.75 pct cu, 27.23 pct Zn, 0.01 pct P11, 0.01 pct re), mall light-gray depnrrits in the form of circular arcs werenoted on the part nf the foil which had been in contact with the single crystal, Fig r. (By superim- approximatetl). These deposits, which, from their color, suggest the appearance of sublimated zinc, were found to coincide roughly with a set of octahedral planes nearly perpendicular to the rod axis. The pattern shorn in the figure held no relation to the profle of the sample since the markin~s on the crystal More annealing werc attributed to traces of cube planes. It seems very likely that the deposits were formed by sutllimation of zinc diffusing from octahrdral planes since diffusian would Eogically take place along planes of maximum atomic spacing. However, it is difficult to understand why a continuous sublimation of zinc should occur from a single crystat in contact with a wrapping roil OF the same composition, and why diffusion would take place along specific octahedral planes and in a regular pattern.

Jan 1, 1949

By Bernard Greifer, Walter Rose

The purpose of this note is to call attention to a source of difficulty which can be responsible for inaccurate estimates of wetting liquid pressure gradients in mixture flow experiments of the Hassler1 type. It has been our experience occasionally to observe what were indicated to be negative pressure gradients, and these were regarded as anomalous in the sense that physically they seemed to contradict the requirement that the flux be in the direction of the potential field. At first it was thought that our scheme of assembling barriers and core sample led to such asymmetry in the distribution of isobars that the manometric leads at each end of the core were responding to internal pressures (within the core sample) which could be either positive or negative with respect to each other, and which in fact might tend to reflect on different effective core lengths in an unpredictable fashion as the wetting liquid saturation was changed. However, no compelling evidence of this possibility has been established. In addition, we were cognizant of the requirements to be satisfied in selecting manometric instrumentation to minimize the delay in response of the manometer to the differential pressures being measured, and were thus assured that our observations of anomalous pressure gradients could not be explained by faulty instrumentation. What we suggest is that if a leak sink occurs in the fluid lines connecting the core to either side of the differential manometer, errors exceeding 100 per cent may result in the estimation of wetting liquid pressure gradient, even though the leak is of such small magnitude that its existence would tend to be obscured by evaporation effects. This is because in a system with leaks at the specified places, the manometer rec- ords at steady state the pressure drop across the manometer barrier elements in addition to the pressure drop across the core sample. This possibility will be illustrated below analytically and by numerical example for the special case where the leak occurs on the high presure side of the core, since we are especially desirous to explain the significance of our observations of the so-called negative pressure gradients. It will be indicated, however, that leak sinks on the low pressure side of the core can account for observations of anomalously high values of pressure gradient, and that multiple leaks on both sides of the core can provide for some compensation so that the errors in pressure estimation are reduced. However, the major point to be emphasized is the fact that the impractical-ity of detecting the small leak sinks which give rise to the difficulties makes it a complicated task for the experimenter in a particular case to know with certainty that his estimation of pressure gradient lies within the limits of error which can be tolerated. Fig. 1 shows the electrical analog of the flow system we have employed in our studies. The inflow and outflow barriers. Rbl and Rb2, the manometer barriers, Rm1, and Rm2, and the core sample, Rc— for a particular fluid saturation and distribution— are all designated as resistance elements; the flowmeter is designated by an ammeter, A; the pressure source is designated by E; and the manometric device is designated by the voltmeter, V. Included in the circuit are the variable resistances, Rx and Ry, which may be regarded as the leak sinks, and which, in general, can vary in magnitude from zero (i.e., a large hole or shunt in the system) to infinity (i.e., no

Jan 1, 1950

By Paul B. Crawford, Melvin B. Burton

A procedure is given which describes how the gelatin model may be-used to study the effect of mobility ratio on areas swept before and after breakthrough in fluid injection programs. Differences in mobility ratio are achieved through the proper selection of electrolytes for the invading and displaced fluids. The progress of the front is followed visually and photographed or traced onto plates (it desirrd positions before and after breakthrough. Example applications to standard flooding pattrrrls, vertically and horizontally fractured reservoirs and the in-situ combustion recovery process ore presentrtl. INTRODUCTION In water flooding, gas cycling and other fluid injection programs, the sweep efficiencies and swept areas after breakthrough are known to depend on the mobility ratio. Previous investigators have described the application of the X-ray technique, stepwise use of the poten-tiometric model and numerical procedures for studying these problems.1,3,4,6 Others have described the application of the electrolytic and gelatin models for studying sweep efficiencies at a mobility ratio near one.2,5,7,8,9 It is a purpose of this paper to describe a procedure for using the gelatin model to study swept areas at mobility ratios other than one. PROCEDURE The technique developed for gelatin model studies is composed of four phases: the construction of the model, the selection and preparation of electrolytes, the running procedure, and the recording of the swept areas. Each phase is discussed independently in order that the over-all procedure will not be confused. Construction of the Model Since some of the advantages of the gelatin model are its economy, and speed, it is desirable to have as small a model as is possihle without creating error through the inability to follow visually the progress of the colored front. For this work, it was found that a distance of 4 to 6 cm between salt bridges is convenient to use. Since the size is relatively small, it follows that the gelatin layer must be thin. For this study, 1/8 in. was used as the gelatin thickness in each case. The model was constructed on a flat 1/2-in. plastic (Lucite) base with boundaries constructed from 1/8-in. plastic strips. The well pattern to be studied was outlined with the 1/8-in. plastic strips on the base with narrow apertures (- - 2 mm) in the boundary to represent the wells. Behind each well opening, a rectangular area of some 8 to 12 sq cm was outlined by additional plastic strips. The plastic strips were fastened to the base by any suitable non-conducting cement so that the boundary system was liquid tight. The electrodes were constructed from sheet copper in a fashion that would allow easy removal. In this work, it was found that by simply forming a large U-shaped clip from a strip of the copper that would slip over the boundary was satisfactory and easily removed. The electrodes should be as wide as one of the sides of the rectangular area behind the well opening. If a fractured pattern is studied, fractures inside the well pattern may be represented by strips of copper of the desired shape mounted in some easily removable fashion. The reason that apertures (or salt bridges) were used for wells instead of metallic electrodes is that the plating of the electroactive ion at the cathode and the introduction of an electroactive ion at the anode has a detrimental effect on the swept area outline if these operations \rere permitted to be carried on within the well pattern itself. The anode may be used within the well pattern

Jan 1, 1957

By A. K. Schellinger, R. D. Lalkaka

IF the ball mill is considered only from an energy standpoint, it can be thought of as a converter of kinetic energy into heat energy and surface energy. The law of the conservation of energy must apply to the ball mill as it does to any machine or process in nature. The heat energy output of the ball mill is apparent to any casual observer of the operating mill since the outflow pulp will be appreciably warmer than the inflow water and rock. The rock in the ball mill is crushed by shearing of its ionic bonding caused by some impact-induced stresses beyond the elastic limit. As the bonds holding the mineral crystal lattices together are ruptured, new surface area is created on each unit of which a definite number of unsaturated bonds exist. Such unsaturated energy of bonding may be termed the "surface energy," and is a potential energy figure. This created energy was withdrawn from the ball mill system and represents an absorption, or disappearance of heat. To reduce the size of the rock, surface area must be created and with it the at- tendant characteristic surface energies of the minerals concerned. Thus the creation of surface energy, from an energy viewpoint, is the creation of useful work by the ball mill. Because of the controversial nature of the energy efficiency figures for modern operating ball mills, it seemed worthwhile to approximate the ordinary magnitude of such efficiencies from the above viewpoint. This was done by an energy balance of the three aforementioned forms of energy, kinetic, heat, and surface energy, for two 9Y2x10-ft grate-type ball mills grinding cement raw materials. Kinetic energy input to the balls was approximated as closely as possible while the heat energy output was measured by means of a thermometer and water and rock flow rates. The assumption was made

Jan 1, 1952

By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic' displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. 'To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard's Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By H. Krueger, H. N. Hersh

USE of autoradiography in diffusion studies offers the advantage that no repeated sectioning is necessary and that the analyses are performed in a simple manner over the continuous range of penetration depths. As part of a program of solid-state physics, it was desired to develop the autoradio-graphic method' quantitatively for use in diffusion studies. Results are reported here for the self-diffusion of silver. Silver was chosen because the existing data are good enough to evaluate the technique." The silver used in this investigation was obtained in the form of ¼ in. diam rods of polycrystalline material, 99.99 pct purity. The radioactive silver, Ag110 (ß, y), was obtained as the nitrate and converted to the chloride for use in a standard cyanide plating bath. The diffusion specimens were 1/2 in. lengths of the rod. They were mounted in bake-lite and the exposed circular face carefully ground and polished. Prior to electrodepositing radioactive

Jan 1, 1956

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961