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By J. M. Smith, D. Kunii

Effective thermal conductivities of sandstones filled with stagnant fluids were measured using a steady-state technique. Data were obtained for seven sandstone samples, taken from four different locations and ranging in permeability from 18 to 590 md. The measurements with gases (helium, nitrogen, air and carbon dioxide) covered a pressure range from 0.039 psia to 400 psig. Data were taken for four liquids — n-heptane, methyl alcohol, 79.8 weight per cent glycerol-water solution and pure water at atmospheric pressure. The experimental results were used to evaluate the theoretical equations for predicting stagnant conductivities developed earlier 4 The low-pressure measurements permitted evaluation of the consolidation parameter bpDp/ks (necessary to utilize the theory) for the various types of sandstones. Using these characteristic values, the tbeoretical equations correlated well with the experimental conductivity data for the several fluids and rock samples. INTRODUCTION An aspect of heat transfer in solid-fluid systems of considerable current interest is the effective thermal conductivity of porous media. The stimulus for study of the subject arises from the need for sound procedures for designing thermal methods of petroleum production. The general system occurs when there exists a flow of fluid through the pores of the solid material. However, a logical starting point in developing a theory for predicting the effective thermal conductivity in the general system is to attack the special case when the porous solid is filled with stagnant fluid. Since the flow rates anticipated in thermal production processes are very low, such stagnant conductivities k,O are also of practical significance. Kunii and Smith4 recently reviewed the existing data for stagnant conductivities and proposed a theory for heat transfer in porous rocks. This leads to equations for predicting the stagnant conductivity as a function of the properties of the fluid and solid phases. The existing experimental information1-3,5,7,8 covered a range of porosities and agreed well with the theory. However, the available data were insufficient to examine critically the effects of two important properties on koe, — the thermal conductivity of the fluid and the pressure. The objectives of the present study are twofold: (1) to measure the effect on koe of (a) the pressure for gases, and (L) the thermal conductivity of the fluid kg for bloth gases and liquids; and (2) to determine for rocks of different porosities and permeabilities the apparent solid conductivity ks and the consolidation parameter bpDp/ks required in applying the theoletical equations. Measurements extrapolated to zero pressure are helpful in evaluating ks and the consolidation parameter. However, the extrapolations must be based upon data obtained at low pressures because in small pores the molecular conductivity of the fluid may be unusually depressed. This occurs when the mean free path of the molecules is of the same order of magnitude as the pore diameter, that is, in small-diameter pores at low pressures. The phenomenon has been studied recently by Schotte6in beds of unconsolidated fine particles. With particles in the size range of 45 to 200 microns, a significant reduction of kg with pressure was found even at absolute pressures greater than 1 atm. In the sandstones employed in the present investigation, pore diameters lower than those experienced by Schotte are likely, so that the effect would presumably be greater. SCOPE OF MEASUREMENTS Stagnant conductivities were measured for four types of sandstones using a total of seven samples. The characteristics of the samples, including porosity and permeability values, are given in Table

By L. K. Nemeth, H. T. Kennedy

The investigation presented in this paper was performd to develop a relationship between the dewpoint pressure of a hydrocarbon reservoir fluid and its composition, temperature and characteristics of the heptanes-plus fraction. This is part of an over-all program to develop correlations for the essential properties of reservoir fluids with the composition, temperature and pressure. In all, 579 dewpoint pressures, determined experimentally on 480 different condensate systems along with their compositions and temperatures, were obtained from the literature and from previously unpublished sources. Compositions were expressed in terms of mol fractions of methane through heptanes-plus, nitrogen, carbon dioxide and hydrogen sulfide, and the molecular weight and specific gravity of the heptanes-plus fraction. Distribution of the samples assured a good representation of most of the major oil-producing areas in the world. A multiple regression analysis program written for the IBhl 7094 digital computer was used to compare numerous equations and to calculate their coefficients. The final equation containing 11 coefficients resulted in an average absolute deviation of 7.4 percent for all the samples. Segregation of data on the basis of one or more variables did not materially improve the results. The correlation developed is useful in predicting the dewpoint pressure of condensate reservoir fluids from variables normally measured in the laboratory. INTRODUCTION In any discussion of the dewpoint of hydrocarbon mixtures, it should be noted that there are two kinds of dewpoints which must be distinguished. The first type, or normal dewpoint, usually occurs at low pressures as dry gas is compressed to the point where liquid first forms. The second type, sometimes called the retrograde dewpoint, occurs when a gas mixture containing heavy hydrocarbons in solution is depressured until a liquid is formed. The first type, as applied to condensate mixtures, would normally be below atmospheric pressure and would be of no interest in reservoir performance. The second type is of great significance in interpreting reservoir behavior and is the property referred to throughout this paper. Laboratory measurement of dewpoints is laborious, expensive and subject to many errors, and it is desirable to find a reasonably accurate method to predict dewpoint pressures from the composition and other readily available properties normally measured on the fluids. A possible method of calculating dewpoint pressures would be to employ a set of equilibrium ratios (K-values). 1 However, the K-values themselves depend on composition as well as temperature and pressure; presently their use adds nothing to the accuracy of predicting dewpoints. If future correlations provide a significantly better method of estimating K-values for heavy hydrocarbons, they may be of greater use. REVIEW OF LITERATURE In 1944, Olds, Sage and Lacey 2 studied the behavior of fluids from the Paloma field. Properties of seven mixtures were studied at temperatures ranging from 100 to 250 F and at pressures up to 5,000 psia. From the information obtained, the influence of composition and temperature upon the dewpoint was determined. It was found that removal of the intermediate molecular weight components from the mixture resulted in considerable increases in the dewpoint pressures. Results indicated that the effect of changes in temperature was relatively minor when compared with the effect of modifying the mixture by removing the intermediate components. Thus, removal of propane and butanes resulted in an increase in dewpoint pressure more than 10 times greater than a change in temperature from 100 to 250 F. The authors stated that althouah

By C. S. Land

Relative permeability functions are developed for both two- and three-phase systems with the saturation changes in the imbibition direction. An empirical relation between residual nonwetting-phase saturation after water imbibition and initial nonwetting-phase saturations is found from published data. From this empirical relation, expressions are obtained for trapped and mobile nonwetting-phase saturations which are used in connection with established theory relating relative permeability to pore-size distribution. The resulting equations yield relative permeability as a function of saturation having characteristics believed to be representative of real systems. The relative permeability of water - wet rocks for both two- and three - phase systems, with the saturation change in the imbibition direction, may be obtained by this method after properly selecting two rock properties: the residual nonwetting-phase saturation after the complete imbibition cycle, and the capillary pressure curve. INTRODUCTION Relative permeability is a function of saturation history as well as of saturation. This fact was first pointed out for two-phase flow by Geffen et al. 1 and by Osaba et a1.2 Hysteresis in the relative permeability-saturation relation also has been reported for three-phase systems.3 Since saturations may change simultaneously in two directions in a three-phase system, four possible relationships arise between relative permeability and saturation for a water-wet system. The four saturation histories of this system were given by snel14 as 11, ID, DI and DD. I and D refer to the direction of saturation change (imbibition and drainage), with the first letter of the symbol indicating the direction of change of the water phase. As used in this paper, the second letter of the symbol refers to the direction of saturation change of the gas phase, i.e., D and I indicate an increase and decrease, respectively, in gas saturation. Only a few three-phase relative permeability curves have been published. Leverett and Lewis5 published three-phase curves for unconsolidated sand, and Snell4 reported results of several English authors for both drairrage and imbibition three-phase relative permeability of unconsolidated sands. Three-phase relative permeability curves for a consolidated sand were published by Caudle et a1.3 for increasing water and gas saturations (ID). Corey et a1.6 reported drainage (DD) three-phase relative permeability for consolidated sands. Recently, Donaldson and Dean7 and Sarem8 calculated three-phase relative permeability curves from displacement data on consolidated sands, also for saturation changes in the drainage direction. The only published three-phase relative permeability curves for consolidated sands with saturation changes in the imbibition direction (11) are those of Naar and Wygal.9 These curves are based on a theoretical study of the model of Wyllie and Gardner 10 as modified by Naar and Henderson.11 Interest in three-phase relative permeability has increased recently due to the introduction of new recovery methods and refinements in calculation procedures brought about by the use of large-scale digital computers. The scarcity of empirical relations for three-phase flow, and the experimental difficulty encountered in obtaining such data, have made the theoretical approach to this problem attractive. RELATIVE PERMEABILITY AS A FUNCTION OF PORE-SIZE DISTRIBUTION Purcell used pore sizes obtained from mercury-injection capillary pressure data to calculate the permeability of porous solids.12 Burdine extended the theory by developing a relative permeability-pore size distribution relation containing the correct tortuosity term.13 The works of Purcell and Burdine were combined by Corey14 into a form that has

Jan 1, 1969

By R. R. Goddard

By use of the frequency response method with a radioactive tracer, it was possible to determine fluid dispersion and distribution in a natural consolidated and an unconsolidated medium. Measurements were made in a linear flow system at oleic saturations of 69 per cent in the consolidated medium, and 100 per cent in both media. Dispersion and distribution were obtained by measuring the amplitude attenuation and the phase velocity of sinusoidal waves with a dual monitor apparatus. The gamma ray emissions permitted in situ measurements at any distance along the porous samples. One result of importance was that the effective diffusivity increased as the wave length increased. As a consequence, a dispersion coefficient appropriate for the injection of large slugs might exceed the value measured by use of small slugs. Since flow models based solely on fluid velocity and an effective diffusivity coefficient imply that the diffusivity should be independent of frequency, such representations were not adequate for the data of this study. A comparison was made with a capacitance model of porous media with deadend PVs, but even this model was not completely adequate. By using attenuation and phase velocity data, fluid dispersion can be predicted without postulating a differential equation satisfied by the tracer concentration, thereby eliminating the need of a complicated model to represent dispersion. INTRODUCTION The flow of similar miscible fluids through a porous medium can be fairly adequately described by two parameters: the average fluid velocity and the effective diffusivity.1-3 It has been pointed out recently, however, that significant discrepancies exist between this representation and the experimental data.4-7 An improved agreement can be obtained by introducing additional parameters based on the concept of dead-end pores. The purpose of the present investigation was to find out whether the frequency response method could be used to measure the relevant parameters. The method was used in the following form. A stream of fluid was flowed at a constant rate through a sample of porous material and the concentration of a radioactive tracer in the fluid was varied sinusoidally at a fixed frequency. The effects of flow through a porous medium are a decrease in the amplitude of the concentration wave and an increase in the velocity of the peaks of the waves above the average velocity. Attenuation and phase veIocity of the waves were measured as a function of frequency and fluid velocity. The simple two-parameter model implies that the diffusivity should be independent of frequency. Data reported in this paper show that the diffusivity decreases as the frequency increases. Hence, as shown also by many others, the two-parameter model is not completely adequate. Coats and Smith 5 used two additional parameters in their model: the volume of the dead-end pores and the rate of mass transfer between dead-end pores and the flowing stream. Their capacitance model of a porous medium containing some stagnant fluid, to which transfer occurs by molecular diffusion, did not explain the dispersion results of either the present study or of theirs. Instead, the capacitance effect can be better described as the result of extreme velocity variations within the pores of the medium, with transfer between the velocity zones by convection. EXPERIMENTAL PREPARATION OF POROUS MEDIA Data reported here were obtained with a natural Berea sandstone, and with two packings of 20/25 mesh sand. Pertinent information about these media is listed in Table 1. The sandstone core was first sealed with a non-

Jan 1, 1967

By N. E. Garner

Laboratory experiments were conducted to investigate the cutting of a single diamond on limestone and shale under simulated down-hole conditions. A high-pressure chamber was modified by adding a rock-rotating device so that planing tests could be run. Weight on the diamond, diamond geometry and differential pressure across the face of the rock were varied. It was found that (I) high differential pressure reduced the volume of rock cut by the diamond at a given bit weight by strengthening the rock and changing the mode of failure; (2) a finely powdered rock left in the bottom of the grooves reduced the volume cut by as much as 50 percent; and (3) orientation of a single diamond about the axis of a drill point had considerable influence on diamond cutting efficiency. INTRODUCTION Diamond bits consist of many diamonds held in a matrix provided with water courses for fluid passage to clean, cool and lubricate the diamonds as they drill formation. Each diamond contributes its share to the overall effectiveness of a bit, but a lack of understanding of the performance of a single diamond has hampered efforts to engineer improvements in diamond bits. The need for those improvements prompted this study. This paper describes the findings of a laboratory investigation of the outting action of a single diamond where the differential pressure between the wdlbore and formation, diamond geometry and vertical force on the diamond were independently varied. The tests were conducted in a pressure chamber that provided relative horizontal motion (planing) between a rock and diamond under simulated down-hole pressure conditions. EQUIPMENT HIGH-PRESSURE CHAMBER WITH ROTATING DEVICE The high-pressure chamber used in previous rock mechanics studies' was modified for this study by addition of a rock-rotating device. The modified chamber (Fig. 1) differs from the old chamber in that the rock can be rotated to provide relative horizontal movement between the rock and the penetrator which may be a small element of a diamond or a drag bit. In this study the penetrator was a single diamond. The rock sample holder inside the chamber is mounted on a thrust bearing and is connected to the external drive mechanism by a stem that passes through two seal elements. The seal elements are needed to allow formation pressure to enter the bottom of the rock sample through a small hole in the stem. The Kapseal seal elements (Tefion boots backed by O-rings) provide low friction (hand free) even at differentials of 5,000 psi. The drive mechanism is a variable-speed transmission with a speed range from 0 to 30 rpm and an output torque of 2,800 in.-lb. A right-angle-drive gear box couples the drive to the stem. The new design has two independent pressure systems (formation and borehole) to simulate down-hole rock stress environment. Formation pressure enters from the bottom of the rock through a 6-in. diameter area, and borehole pressure acts over the remaining surface. A 14-in. layer of zero fluid loss oil-base mud poured over the top of the rock and an O-ring seal on bottom allow a differential between the borehole and formation pressures. Bayol 50 was used as the hydraulic fluid in the chamber. The differentials reported here were obtained by elevating the borehole pressure while keeping the formation pressure at zero.

By D. A. Flanagan, B. L. Landrum, P. B. Crawford, B. C. Norwood

Herern is described a heat conduction model which has been developed to predict the pressure distribution within a reservoir being subjected to rrnsteady-state depletion. Although potentiometric models have been widely used to study reservoir pressure distribution, their application is limited to the study of steady-state cases. Electrical analyzers may be used to study unsteady-state phenomena, but their application and simulation have certain limitations. Much of the now accepted theory of unsteady-state fluid flow in porous media has evolved from previous heat conduction knowledge. An analogy between the flow of fluid in an unsymmetrical reservoir and con-duct ion of heat in a similarly shaped unsymmetrical metal plate is made to show adaptability of the hear conduction principle to transient reservoir cases. A description of the model and necessary instrumenrarion is included. Data show influence of well location on pressure distribution during unsteady-state deple[ion. Application of results is made to a hypothetical reservoir and to a reservoir located in an irregular aquifer. INTRODUCTION Development of methods for predicting behavior of petroleum reservoirs has resulted partially from adaptation of electrical and thermal flow concepts to the flow of fluids through porous media. Extensive investigation of electrical and thermal flow problems has resulted in mathematical solutions applicable to many reservoir problems. The relative ease of measuring electrical flow has brought wide acceptance of the use of the potentiometric model to study certain field problems. Potentiometric models are restricted to the study of steady-state conditions because of the instantaneous response of electrical flow to changes in the applied potential. The electrical reservoir analyzer has been one of our most useful instruments for studying certain phases of unsteady-state behavior1. Other than approximation techniques, no method exists for determining pressure distribution in an irregular reservoir during primary depletion. Heat flow, like fluid flow, is inherently transient. The model described here was developed to use this transient nature of heat flow, measurable in the laboratory, to simulate transient flow of fluids in the porous medium of the reservoir above the bubble point. A metal plate shaped like the reservoir to be studied was heated by a "well" source. Temperature increase in the plate is analogous to pressure decline in the field if the field is being depleted, or pressure increase if fluid is being injected. This study is intended to determine the feasibility of using the transient nature of the heat flow to study the transient behavior of fluid flow. It is hoped that this new technique will aid in the understanding of one of the more complex phases of reservoir engineering. THE FLUID FLOW-HEAT CONDUCTION ANALOGY The similarity of the equations which describe the flow of fluids through a porous medium and the conduction of heat through a solid is well known2. Rate of flow of fluids is given by Darcy's law3. while the rate of flow of heat is given by Fourier', (I,, - KA 4T........(2) Combining Eq. 1 with the equation of continuity for a compressible liquid", i.e.,results in Expressing y in terms of the compressibility, i.e., pr = peey ,..........(5) and by expanding the exponential and neglecting higher orders of cp one can obtain

By W. T. Turrall, M. J. Cook

A discussion of modern developments in beneficiation of fine sizes of anthracite, this paper includes a description of the plant flowsheet, an analysis of operating results, and a summary of fundamentals of mineral separation relative to plant operation. DURING the past several years Lehigh Naviga-tion Coal Co. has installed equipment at Tamaqua and Lansford collieries for cleaning and sizing No. 4 buckwheat —3/32 + 3/64 in. and for recovering and cleaning flotation coal —20 + 200 mesh at Tamaqua colliery. Papers describing some of these installations have been presented to AIME. At Coaldale colliery, however, methods used to clean fine coal were inadequate and inefficient. Management decided upon a thorough investigation of all existing processes before building a plant to treat the combined three sizes mentioned. Investigation, carried out on company property and at other plants, entailed a study of hydrotators, hydroclassifiers, tables, spirals, flotation machines, methods of screening, and methods of dewatering. On the basis of this investigation a flowsheet was designed which necessarily excluded many processes in use, and the writers wish to emphasize that no criticism is implied by omission of processes or machines. A determining factor in selection of many machines was the policy of standardizing equipment wherever possible. Flowsheet and Operational Data The first principle to be considered in designing of any plant is efficiency of cleaning as related to laws of classification. Beneficiation of coal may be described as separation of two materials having different specific gravities. Although there is an inherent ash content even in the purest coal which slightly affects its specific gravity, it is recognized that many particles are true middlings. The percentage of these particles allowable in the final product depends upon the ultimate ash, or specifications of the consumer. Richards in his study of free settling and hindered settling classification' determined that particles of equal size and different specific gravities had unequal settling velocities. He also determined a definite size relationship for equal settling velocities with free settling and hindered settling conditions. Considering the design of machines used to clean No. 4 and No. 5 buckwheat, it may be assumed that both free settling and hindered settling conditions exist and that ratio of size for practical operations is between the established values. The essential factor is that the more efficiently and closely sized the feed is maintained, the more nearly perfect the resulting separation. Flowsheet design was governed primarily by factors related to the 1200 to 1500 tons per hr feed to the main plant. It should be stressed that because of the many sources of supply from mine and stripping, the physical characteristics of this feed varied considerably. The most significant influence was varying percentage of fines, necessitating that all machines be capable of operating under maximum peak load during periods of surge. Since cleaning practice is a wet process, about 9000 gal per min containing 14 to 15 pct solids, or 350 tons per hr, must be treated. This slurry contained all the fines, or —3/32 in., but also percentages of oversize, up to 1 % in., dependent on spills or breaks in screen jackets, a not uncommon occurrence in preparation plant practice. The flowsheet developed is shown in Fig. 1. Circled numbers represent points of sampling. Table I gives operational data including size, ash by size, composite ash, rate of flow in gallons per minute, percent solids dry weight, and average tons of solids per hour. It should be noted that these results are subject to human error in sampling practice. Detailed information reported is a representative evaluation of plant operation.

Jan 1, 1954

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.'-' Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.' There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the ''vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By Bunting S. Crocker

Bunting S. Crocker (Executive Vice President, Kilborn Engineering Ltd., Toronto, Ont., Canada)-This is an interesting report on laboratory-scale testing with pebble charges in 12-in.-diam mills, and the author correctly concludes that useful laboratory testing can be done. In the opening paragraphs he states, "laboratory pebble-milling tests have been considered too difficult to perform and not relevant enough to the actual grinding situation"!! This is definitely not so! The writer published detailed tests done in a 12-in.-diam mill comparing pebble and steel balls in 1952 6 and again in 1954 7. We note that our review paper in 1963 was the only one mentioned in the References. The author states that "a smooth lining is more frequently used in commercial-scale pebble grinding." The writer has designed some 22 plants treating 134,000 tpd in North America and Australia. He has also visited pebble installations in Norway, Sweden, Finland, and South Africa. All these plants correctly use heavier lifters than would be considered standard for ball mills of a similar size. Smooth liners are not recommended in wet ore treating plants. In the 1952 paper6 it was clearly demonstrated in the test work that the individual ore pebbles had to be the same weight-not the same diameter or size-as the steel balls if comparable grinding results were to be obtained. In the tests performed in this study most of the pebbles "passed 50-mm round hole screen openings and remained on a 40-mm round hole sieve. Correspondingly most of the ball mill experiments were performed with 50 or 40-mm steel balls". Thus, the balls and pebbles were essentially the same size or diameter. This means we are comparing apples and oranges. When the feed being ground is fine enough the pebbles will be superior. When the feed is coarse the steel balls will be the better. This is similar to grinding tests in which two sizes of steel balls are compared. In the middle of the article, "Crocker5 has reported that equal weights of pebbles and steel balls achieve the same grinding capacities under similar conditions …", then he proceeds to question this postulate. In the eight reports that I have published, I have never made this statement. What I have said is "for comparable grinding, the individual pebbles in the mill charge should be the same weight as the individual steel balls." This is not the first time that I have been misquoted on this point! It is most unfortunate that this test work has been done with a ball and pebble of the same diameter and not the same weight. It is impossible to properly evaluate the results. I also regret the fact that the screen analyses of the tests were not shown. Many of us who have been 40 years or less in the grinding game can easily read screen analyses at a glance. We can tell whether the top meshes are being ground by the ball charge, etc., etc. The graphs are fine for the summary or to illustrate conclusions but are often misleading in the report itself. However, we do agree that useful pebble grinding tests can be done in a 12-in. mill.

Jan 1, 1973

By W. L. Worrell

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By F. H. Ellinger

TI HE crystal structure of neodymium has been re-A ported by Quill1 and by Klemm and Bommer"s to be hexagonal-close-packed, Strukturbericht-type A3, with a, = 3.650.4, c, = 5.890.4, c/a = 1.614. Klemm and Bommer,% owever, pointed out that the observed intensities of the lines of the neodymium powder pattern agreed only in part with the intensities calculated for the type A3 structure, and that the neodymium powder pattern showed extra lines which could not be traced to impurities. They found that these extra lines could be accounted for by doubling the c-axis, but apparently they did not consider their evidence to be sufficiently conclusive to justify reporting the doubled c-axis. In the present work, the structure of neodymium was found to be double hexagonal-close-packed. The neodymium metal used in the present investigation was obtained through the courtesy of F. H. Spedding of the Ames Laboratory. Its major impurity was stated to be 0.03 pct Ca. The author's spectrographic analysis indicated high purity and carbon was determined to be less than 30 ppm. X-ray powder specimens were prepared from filings stress relieved in vacuum at 200°C for 50 hr. Powder photographs were taken in an 114.6 mm diam camera (Straumanis film mounting) at room temperature and in a 19 cm diam Unicam high temperature camera at elevated temperatures. Copper x-radia-tion was used for all the photographs. The powder pattern of neodymium was found to index to a hexagonal unit cell with dimensions, as determined from the high angle Ka doublets, of: a.= 3.655+0.001.4; c, = 11.796+0.004.4; and c/a = 3.227 at room temperature. The measured density of neodymium shows that this cell contains 4 atoms, the calculated density is accordingly D, = 7.02 g per cu cm. The diffraction data for the first 15 lines of the powder pattern are listed in Table I. In a double hexagonal-close-packed unit cell, the 4 atoms would be in the positions (0,0,0), (0,0,%), (1/3, 2/3, 1/4), and (2/3,1/3,%) of space group P 6,/mmc. On the basis of these positions, the relative intensities of the reflections were calculated using the expression: 1+cos2 20 I oc \Frp 1 ' sin2 0 cos 0 where F is the structure factor and p is the multi- plicity factor. Since absorption was not taken into consideration, comparison of observed and calculated intensities should be made only for neighboring reflections. Each atom has 12 neighbors, 6 in the basal plane at a distance of 3.655.4 and 3 above and 3 below at the closer distance of 3.626.4. These distances correspond to an average radius of the neodymium atom of 1.820.4. The description of this structure in terms of A, B, and C close-packed layers of atoms is ABAC ABAC. ...... The structure repeats every fourth layer and the stacking sequence of the second, third, and fourth layers corresponds to cubic-close-packing of atoms. A series of powder photographs taken at successively increasing temperatures up to 680a10"C revealed that the double hexagonal-close-packed structure is stable up to this temperature. Acknowledgments The authw wishes to thank W. H. Zachariasen and A. S. Coffinberry for their helpful comments on this work and also Marion Gibbs for measuring the diffraction films. This work was sponsored by the United States Atomic Energy Commission.

Jan 1, 1956

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By N. T. Cotman, C. H. Pickering, P. B. Crawford

A beat-conduction model has been developed to study the flow of fluids in a stratified oil reservoir which is being subjected to unsteady-state depletion. To simulate stratification, plates of different metals were joined together so that cross flow could occur between strata. A description of the model, plate construction and necessary instruments is included. The data indicate that stratified oil reservoirs experiencing cross flow may be treated as a single, homogeneous, producing sand having properties intermediate between those of the layers making up the system. A technique for averaging core-analysis data to arrive at the proper average value of rock permeability and porosity is presented INTRODUCTION Although oil has been produced from reservoirs for 100 years and reservoir injection processes have been undertaken for 40 years, the industry is still inadequately informed on the problem of reservoir inhomogeneities. Stratification is perhaps the best-known type of reservoir heterogeneity. Urenl discussed the possible significance of this nonuniformity in his 1927 paper on the theoretical aspects of water flooding. Since this time the problem of vertical permeability variations has been the subject of much discussion and numerous papers. Levorsen2 simply describes the origin of layered beds in his Geology of Petroleum. Some beds are field-wide and may be traced from well to well, while others apparently pinch-out and become discontinuous. In addition, the physical characteristics of a layer may vary from place to place. For these reasons, a stratified system is not easily defined. In calculations involving oil reservoirs in which permeabi1ities vary, methods presently used contain many simplifying assumptions. The reservoir frequently is considered as consisting of permeable layers, each of uniform vertical and lateral permeability and each behaving as if separated from adjacent layers by thin impermeable layers. Other assumptions frequently made in reservoir calculations are steady-state flow conditions, unit mobility ratio, linear geometry, average or homogeneous porosity, and negligible capillary-pressure and gravity effects. Muskat3 has. developed solutions to the stratification problem for mobility ratios other than unity for both linear and exponential permeability distributions. He assumes lateral uniformity and continuity of all productive strata and does not consider porosity. This study will take into account transient effects, cross flow and varying porosity, as well as the variations in permeability, by means of a heat analogy. Muskat5 has shown the similarity of the equations which describe the flow of fluids in a porous medium to the flow of heat through a solid. Landrum, et al,6 made an analogy between the flow of fluid in an unsymmetrical reservoir and the conduction of heat in a similarly shaped metal plate. This analogy is summarized briefly as follows. If fluid is produced from an oil reservoir above the bubble point, the resulting pressure distribution will be identical to the temperature which would result in a metal or heat-conducting plate if heat were similarly removed. This means that a study of heat flow in stratified thermal models will behave like fluid flow in stratified oil reservoirs. For mathematical correspondencies, set- Ref. 6. The fluid mobility k/p is proportional to the thermal conductivity, and the porosity-times-compressibility product is proportional to the density times specific heat of the thermal plate. EXPERIMENTAL EQUIPMENT AND PROCEDURE The stratified reservoir model used in this study is illustrated schematically in Fig. 1. A Leeds and Northrup Speedomax Type G temperature recorder

By P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the annealing texture of highly rolled aluminum consists of the four retained components of the rolling texture near (123) [121], rather more sharply developed, and of a cube texture component. Local reorientation corresponds fairly well to 40 rotation around a [111] axis. In copper strip rolled 96 pct, the annealing texture is mainly the cube texture, with the four twin orientations as minor components. The annealing texture of highly rolled brass strip consists of four components of the (225) [734] type. REVIEWS by Wassermann,' Barrett,' Dunn,3 and Richards' give detailed accounts of the numerous publications dealing with annealing textures in rolled polycrystalline metals. Although a considerable amount of information of an empirical nature has been available for many years, even relatively recently the state of recrystallization-texture theory was considered uncertain. The reviews referred to above deal mainly with the description of experimental results, without developing generally applicable principles, suitable for explaining the observed annealing textures. The investigations of Burgers and Louwerse5 and Barrett6 showed that in deformed single crystals of aluminum the orientation of the recrystallized grains deviates drastically from that of the deformed matrix. According to Barrett and to Beck and Hu,7 the relationship between the two orientations can be best described as a rotation of about 40° around a [111] axis. Recent investigations led to similar orientation relationships for various face-centered cubic metals with a simple texture, regardless of whether the annealing process was recrystallization (strain-free grains growing in a highly deformed large crystal of aluminum' or copper: or in deformed cube texture copper") or coarsening (strain-free grains growing at the expense of an essentially strain-free, fine grained, polycrystalline matrix of single orientation texture copper,'" aluminum,' or nickel-iron). Barrett" pointed out the possibility that this orientation relationship may be a result of the orientation dependence of the rate of grain boundary migration. More recently, considerable evidence became available in favor of this view.12,13 In apparent contradiction to the above results, it has been known for a long time that the recrystallization texture of polycrystalline metals is often similar to the deformation texture. This was found, in particular, for the fiber textures obtained by wire drawing, compression, or compression rolling.' Following a suggestion by Barrett,2 Kronberg and Wilson and Beck and Hu7 described a mechanism by which a [Ill] fiber texture, resulting from plastic deformation, may be retained upon recrystallization, even though the orientation of individual recrystallized grains differs from that of the local area of the matrix in which they grow. This mechanism assumes that the reorientation corresponds to a rotation around the [1ll] axis, which is also the fiber axis. The present investigation was undertaken to examine in detail the orientation relationship between deformation texture and recrystallization texture in rolled face-centered cubic metals, using the quantitative methods of texture determination that have recently become available.", '" Quantitative pole figures for the rolling textures of such metals were reported recently." Quantitative pole figures for annealing textures are given in the present paper. It was planned to investigate whether or not the orientation relationship previously found for the recrystallization of deformed single crystals, and for coarsening of single-orientation texture material, is capable of accounting for the observed, often complex, annealing textures in rolled polycrystalline metals. The question whether local reorientation is predominant, even in the early phases of the annealing process, was to be studied with high purity aluminum. by making use of an oxide film and sensitive tint illum-

Jan 1, 1953

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,'who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

By R. C. Gifkins

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By Carle Hayward

IN reheating quenched steel to remove part of the hardness, the softening effect has generally been considered to be a function of temperature and time. The temperature effect is well known, and long before pyrometers were heard of the blacksmith was able to do a good job of tempering, by rule-of-thumb methods and experience in judging temperatures. Modern conditions, which demand steel that will withstand the severest tests, require that the heat treatment he carried out with every possible precaution to secure the best results obtainable. Pyrometers and heat-treatment furnaces of many types are on the market and improvements are continually being made so that it is now possible to regulate the temperature in heat treatment very accurately. There is -still a question regarding the time that the steel should be subjected to treatment. It is customary with all operators to insure the desired tem-pressure throughout the specimen and it is generally supposed that a longer treatment of a hardened steel produces a further softening but there are few published figures showing the exact effect of time of treat-ment at constant temperature. A search of the literature disclosed several brief statements that the tempering effect was a function of both time and temperature, but in no case were any figures given. The opinion is very generally held that the well-known tempering colors are accurate indicators of the degree of tempering. This is disputed by Brearley (The Heat Treatment of Tool Steel, page 102) who states: It has been said that the result would be the same in respect to both hardness and other properties whether the colors were obtained by a shorter heating at a higher temperature or a longer heating at a lower one. This, to say the least, is a very doubtful conclusion, and is certainly not borne out by mechanical tests on oil-hardened and tempered motor car steels, which, after tempering for periods varying from 15 min to 2 hr., show no very great differences. The present investigation had for its object the obtaining of some definite data regarding the effect of time, which might serve as a guide to those engaged in the heat treatment of steel. The Rhode Island Tool Co. cooperated by furnishing the steel and machining the test specimens.

Jan 2, 1917

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

By P. S. Roller

P. S. ROLLER,* College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should be defined as the distance between an F line and a [?] line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and [?] lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. I between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling. It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz," This would require many data to prove, but no proof is given; any considera¬tion would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.,* Cambridge, Mass.¬Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids.5 Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystalline solids. Andreasen and Berg8 have ground

Jan 1, 1941