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By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell's Principles of Petroleum Geology' contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By H. C. Chang, N. J. Grant

Creep of very coarse grained, high purity aluminum was studied at 400° to 1100°F with an initial stress range of 50 to 1200 psi. The process of boundary sliding and migration was studied. The driving force of boundary migration under creep conditions is shown to be a combination of strain energy migrationand surface energy. A theory is presented regarding the strainenergyrole the grain boundaries play under creep conditions. From this thetheory intercrystalline failure of commercial alloys can be explained. Also from this theory an optimum grain size should exist for good high temperature properties of high purity materials. IN the investigation of the creep of very coarse grained, high purity aluminum previously reported,' the cyclic nature of the process of grain boundary sliding and migration has been established by microscopic observation of the actual creep process as well as metallographically. It was also substantiated by measuring localized strains across the grain boundaries. In addition, it was shown how extensive subgrain and fold formation may result from boundary sliding and how the slid grain boundary may become sharply wavy as a result of subgrain formation. Since the publication of those results, additional information on the process of grain boundary sliding and migration has been obtained. It is the purpose of this paper to report on the direction and driving force of boundary sliding and migration, the effect of grain size, and the effect of temperature. Finally the effect of decreasing purity (alloys 2s and 3s) on the process of boundary sliding and migration is noted. From these results, an explanation is presented for the intercrystalline failure of alloys under creep conditions. The effects of grain size on the creep properties of impure and high purity materials are discussed in the same light. The experimental procedures and technique have been presented elsewhere.' It is only necessary to state how the 2s and 3s aluminum specimens are prepared. Machined specimens were first annealed at 600°F for about 12 hr. In order to produce a large grain size the specimens were then stretched 3 to 8 pct. The specimens were marked with reference marks, electropolished, annealed at 900°F for 24 hr and at 1150°F for 12 hr, and repolished. The grain size of 2s aluminum produced by this treatment is comparable to that of high purity aluminum in the direction of its width of the specimen, i.e., there are 2 to 4 grains across the width of the specimen. However, the grains of 2s aluminum are 3 to 10 times longer in the direction of the specimen axis. On the other hand, the grain size of coarse grained 3s aluminum ranges from 10 to 20 grains across the width of the specimen due to the treatment just outlined and therefore is much smaller than that of both high purity and 2s aluminum. As in 2s aluminum, the grains are about 3 to 10 times longer in the direction of the specimen axis than in the direction of the width of the specimen. The arrangements of the grains in 2s and 3s aluminum were generally irregular; therefore it was difficult to follow the course of the grain boundaries. Results Method of Presentation: In order to show the arrangement of the grains, especially the direction and positions of the grain boundaries, traces of the grain boundaries on the four surfaces of the specimens were unfolded and mapped out after macroetching. Figs. 1 and 2 show the structural development drawings of specimens P-3 and P-8 respectively. The two flat surfaces (of which the front one faces the microscope) and the round-edged surfaces will be called the "front surface" and "back surface" and

Jan 1, 1954

By Winthrop P. Haynes

The symposium on production for the year 1944 includes more foreign papers than any one of the past three years, because of a partial relaxation of the censorship in many Western Hemisphere countries. The committee was not successful, however, in securing papers from Europe and the Near and Far East at this time, with the exception of Saudi Arabia and Bahrein. Where possible, these papers include summaries upon production for the missing war years, so that we shall have no permanent gap in the records. At the close of the war, we hope again to publish the usual more complete form of report for all important oil-producing countries. EXCERPTS FROM CIRCULAR TO AUTHORS In order to facilitate interpretation of the data in this chapter, we print the following excerpts from the Circular to Authors. The field is the unit in this tabulation. In cases of fields extending across State boundaries, such as Rodessa, it is suggested that each State author treat the section of the field in his State as a unit, and by a footnote indicate that the field extends into an adjacent State. Each place in the table may represent one of three possibilities; either the proper entry is determinable and can be supplied by the author, or an approximate figure can be supplied which is the author's best guess and should be entered followed by an x, or it does not apply to the particular field and the space is left blank. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. The entry of a zero is a positive declaration, and it is an important declaration where it is in order. It is thought that the nearest whole numbers are sufficiently accurate for our purposes except as to percentage of sulphur in oil. If an author desires to report any other figures to tenths, he may do so. The quantity of gas produced should include, where possible, gas sold or otherwise marketed, and gas blown into the air, burned as flares or otherwise wasted. Segregation of these figures would be interesting if the authors can make such segregation. In any event, the figures should represent as nearly as possible the total quantity of gas removed from the reservoir. . Under the columns on "Depth," the average depth to the top of the productive zones and to the bottom of the productive wells, when subtracted, should give the approximate thickness of the productive zone. For fields where this is not true because of unusually high dip or for some other reasons, it is suggested that the authors indicate in their text the approximate average thickness of the productive zone. The net thickness of the producing formation should be the thickness of the producing zone, less the estimated amount to cover the portions of the zone that do not yield oil, such as dense shales, etc. It is recognized that for some fields the authors can only make rough guesses; in such cases, they should enter their best estimate followed by an x. Average production per acre-foot need not be reported as it can

Jan 1, 1945

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 W. L. Kerlie, J. H. Richards

The variation in hydrogen content of basic open-hearth steels during refining and the effect of changing from steam to air atomization were studied. The water content of the furnace atmosphere, the slag basicity, and the degree of oxidation of the slag-metal system largely control the hydrogen in the steel. SMALL amounts of hydrogen have an adverse effect on the ductility of steel and a wide range of hydrogen contents has an adverse effect on the internal soundness of both ferrous and nonferrous castings. This has been of major concern to the metal industry, both manufacturers and fabricators, for many years. As one of the results of continuing investigations of the hydrogen problem, much has been learned about methods of reducing the hydrogen content of liquid metals below the relatively high levels that are normally associated with such phenomena as rising ingots and excessive porosity in sand casting. However, it was not until a reliable and simple method for sampling and analyzing liquid metal was developed that much progress was possible in quantitatively evaluating the effect of steelmaking practice on hydrogen contents at levels below 6 to 8 ppm. Throughout all the work described in the following presentation the Geffner pintube technique was used to obtain samples of liquid metal1 * and the tin-fusion method, developed at Massachusetts Institute of Technology,2 was used to analyze the samples. Before attempting a systematic experimental program for minimizing the hydrogen content of open-hearth steels, it was necessary to determine the variation in hydrogen in the open-hearth bath during the normal processing of a heat. The logs of ten heats are illustrated in Figs. 1 through 7. The number at each point on the graphs refers to the number of pintube samples analyzed for hydrogen. An increase in the hydrogen content of the liquid metal during the early period of refining is apparent in all heats. There is evidence of a decrease in hydrogen later in the refining period, see Fig. 2, for example. Therefore, the existence of a maximum hydrogen content at some intermediate time during the refining period is anticipated. To test for the existence of a maximum, the data illustrated in Figs. 1 to 5 were grouped together so that they could be examined on a collectively comparable basis. The grouping was effected, as illustrated in Fig. 8, by superimposing Figs. 1 to 5 so that the apparent hydrogen maxima coincided at a fixed position, indicated by the zero on the time axis. Also, by vertical adjustment until the graphs appeared to the eye to be superimposed, the hydrogen scale was made to show the change in hydrogen content. That is, a standard amount was subtracted from the hydrogen values for each heat. Therefore, Fig. 8 represents a generalized presentation of the data and, for this reason, cannot be used to predict the actual hydrogen content of the bath during refining, but rather to show the probable rate of change in hydrogen during refining. Statistical examination of the grouped data in Fi.g. 8 shows that the apparent. increase and suhsequent decrease in hydrogen are real and confirms the existence of a maximum in general. The average increase In hydrogen during the early period of refining is between 0.8 and 1.3 ppm per hr, and the

Jan 1, 1958

By P. E. Baker

An improved method of logging formation density has been developed in which the formation is bombarded with a collimuted beam of gamma rays. By means of a scintillation detector and pulse height discriminator, the gamma-ray energy band is accepted and recorded which corresponds to deepest penetration into the formation. Laboratory tests on a field tool revealed no borehole diameter effect for smooth holes and no effect of formation chemistry, except insofar as chemistry affects density. In extensive field tests, the density log has exhibited satisfactory agree-ment with core measurements and has correlated accurately with other logs. INTRODUCTION This paper describes an improved method of logging formation density by means of back-scattered gamma rays to penetrate the formation together with energy discrimination to select only that energy (or frequency) range corresponding to deepest penetration into the forma- tion. This method of density logging was developed at the La Habra laboratory of California Research Corp.* Field instruments have been built and tested by McCullough Tool Co. and commercial service has begun in some areas. All of the data discussed here were obtained for the original field tool. The density log can be a valuable adjunct to existing logs because of its use in determining porosity quantitatively. It is useful also in connection with seismic and gravity surveys where formation density information is of interest. PHYSICAL PRINCIPLES The intensity, I, of a beam of gamma rays after traversing a distance, x, in an absorbing medium is given by I = loe -ax where I, is the intensity of the beam entering the medium and a the attenuation constant or macroscopic cross section of the medium for gamma-ray absorption. The macroscopic cross section depends on the number and types of atoms per unit volume and the gamma-ray energy. In brief, it is the sum of the atomic cross sections of all atoms per cubic centimeter. The density of the material is the sum of the masses of all atoms per cubic centimeter. Thus, the density and the macroscopic cross section for gam-ma-ray absorption vary in propor- tion to the number of atoms per cubic centimeter. The density of the material increases, of course, if the atomic masses increase without a change in the number of atoms per cubic centimeter. When the density increases in this latter way, the macroscopic cross section increases also, but disproportionately. This results from the fact that part of the gamma-ray absorption arises from the photoelectric effect and the pair-production effect**, which are proportional to the sixth and to the second power, respectively, of the atomic number of the absorber. The remainder of the absorption results from the Compton effect, and is directly proportional to the atomic number. The gamma rays that undergo Compton scattering are not immediately absorbed. Since these rays are scattered in all directions, a fraction will emerge from the face of the medium at which they entered. If a gamma-ray shield is placed between the source and detector, most gamma rays reaching the detector will be those scattered out of the medium. The intensity will depend on absorption and scattering in the medium, and so indicates the density of the medium. For gamma rays for which Compton scattering prevails, the intensity

Jan 1, 1958

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

John Duer Irving, who left his post as Professor of Economic Geology at the Sheffield Scientific School, New Haven, Conn., to join the Eleventh Regiment of Engineers shortly after the declaration of war, died in France, July 26, 1918, from an attack of pneumonia. Through the initiative of Mr. Benjamin B. Lawrence, a memorial service to Captain Irving was held at St. Paul's Chapel, Columbia University, on Sunday afternoon, August 4, which was' attended by members of Captain Irving's family, and about four hundred of his friends from Columbia, Yale, the American Institute of Mining Engineers and the Association of the 11th Regiment of Engineers. Professor James F. Kemp delivered the memorial address, and has prepared for the Institute the following account of Captain Irving's life, Professor Kemp and Captain Irving having been associated on the most intimate terms for a number of years. , The war has brought home to friends and kin in the western shores of thc Atlantic many losses whose suddenness has the shock of a blow. Many more will follow, but none can leave a sharper sense of regret than the news that the keen and productive mind; the inspiring teacher; the successful and considerate editor, the fine, true man and friend had all passed away when John Duer Irving made the final great gift to the service of his country, in the cause of decency and right. In the closing days of July, the cable brought the tidings that toward midnight on the twentieth of the month pneumonia had proved too great a tax upon one already worn by excessive labors. John Duer Irving was born in Madison, Wis., August 18, 1874. His father, Roland Duer Irving, was at the time professor of geology, mineralogy and metallurgy in the State University of Wisconsin.' Roland . Irving, the father, had entered Columbia College in 1863, but trouble with his eyes compelled him to suspend his studies in the classical course in his sophomore year, and to replace study with some months of life and travel in England. Ultimately his eyes became stronger, and he entered the School of Mincs, completing the course for the degree of Engineer of Mines in 1869, with the third class graduated. The class of eleven contained other future geologists. It numbered on its roll Henry Newton and Walter P. Jenney of the early survey of the Black Hills, where John, future son of Roland, was in the course of years to make his doctor's dissertation, and with its publication his really serious entrance into the profession. Roland Irving was a favorite student of Professor J. S. Newberry, affectionately known to all of his students as "Uncle John," and after some experience in mining and smelting in Pennsylvania and New Jersey, joined the Ohio Survey under Dr. Newberry. The work in Ohio was largely performed during the vacations of the University of Wisconsin, to whose chair Roland Irving was called in 1870. Later, his residence in Wisconsin led to two events of prime importance in the history of American geology. He began the study of the Gogebic iron range and caught the clue to the origin and stratigraphy of the iron ores of all the Lake Superior ranges; and he later undertook the mapping and description of the copper-bearing rocks of the Lake Superior basin. The formative years of the son, John, were passed in a home where the father.

Jan 1, 1920

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

By H. S. Wang, Y. P. Gupta

Diffusion of zinc and germanium in liquid silver is measured in the temperature range 975" to 1400°C by use of the capillary-reservoir technique. The ex-perinzental results are discussed in terms of the fluctuation and the "hole" theories of liquid diffusion, assunzing the solute as a point charge equal to the difference in the valences of the solute and solvent atoms. The additional coulombic interaction term due to the excess solute charge is evaluated in terms of the Thomas-Fenni approximation. The theoretical and experimental results agree with both the fluctuation and "hole" theories of liquid diffusion. No perceptible effect on solute diffusion in liquid silver of the size difference between the solute and solvent atoms/ions is apparent. DIFFUSION in liquid silver of electropositive solutes indium, tin, antimony, and homovalent gold has been previously reported by Leak and Swalin1 and Gupta,' respectively. These solutes have nearly the same atomic size but differ principally from one another in excess valence (+2, +3, +4, respectively). The observed differences in the temperature dependence and the rate of solute diffusion were explained in terms of an added coulombic interaction between the solute and the solvent atoms. In the case of diffusion of gold in liquid silver, the data were found to be consistent with an effective valence for gold of -0.85, as proposed by Le Claire.3 Recently, Wang and Gupta4 have reported a study of diffusion of ruthenium, iron, and cobalt in liquid silver. The results of diffusion of these solutes and their temperature dependence were found consistent with the hole theories and the fluctuation theories of liquid diffusion, if ruthenium, iron, and cobalt were diffusing in liquid silver with relative valences -2, -1.3, and -0.5, respectively, instead of -3, -3, and -2 as suggested by the relative position of these elements in the Periodic Table of Elements. Furthermore, the predicted valences for these solutes were observed to be consistent with the sparsely available information on the magnetic properties of some of the dilute alloys of copper and silver with these solutes. In theoretical calculations of solute diffusivity, the solute was assumed as a point excess charge equal to the difference in the valences of the solute and solvent atoms. Both the assumption of a point excess solute charge and the use of the Thomas-Fermi approximation to calculate the potential of a solute charge are less precise for the case of electronegative solutes. Therefore, it was not possible to infer from the data on ruthenium, iron, and cobalt an effect, if any, on solute diffusion of the relative differences in either the Period or the size of the solute and solvent atoms or the solute atoms themselves. A study of the diffusion of Period 4 elements, specifically zinc and germanium was, therefore, undertaken since zinc and germanium, respectively, have relative valences of +1 and +3 in liquid silver and the data obtained on diffusion of these solutes could be compared with the available data on diffusion of Period 5 electropositive solutes, indium, tin, and antimony in liquid silver. From such a comparison, it was hoped to learn something about the effect, if any, of the ion size or the structure of the ion core on impurity diffusion in liquid silver. EXPERIMENT The diffusion of tracer zinc and germanium in liquid silver was studied by the capillary reservoir technique, modified adequately for use at high temperatures. In principle, capillaries containing liquid silver

Jan 1, 1970

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer' and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By D. R. Parrish, V. J. Berry

Reverse combustion is one thermal method of recovering hydrocarbons from porous undergrortnd formations containing oil or tar. In applying this method, air is introduced via an injection well and the mixture of air and hydrocarbons is ignited in the production well. A combustion zone then recedes toward the injection well, counter-current to the air flow. If the combustion-zorie temperature is sufficiently high, the oil or tar irz place is distilled arid cracked. The hydrocnrhon flows as a vapor to the production well and subsequently is condensed at the surface. Maximum temperature and velocity of morcment arc the two dependent variubles defining the progress of the combustion zone. A theoretical analysis has been made of heat flow in the reverse-comhustion process as.srtrning linear flow in a homogeneous system. The differentirll equatious, which include the oxygen-hydrocar-hon rctrction rate, have been solved numerically. Rescllts indicate that the maximum temperature reached and he cornbustion-zone relocity both increase with an incrense in air-injection rote. Heat loss to surroundings has little effect on the maximum comhustion-zone ten?perature achieved, but it is reflected in a reduced com-bustion-zorzc, velocity. It is also predicted that an increase in the oxygen-hydrocarbon reaction rate results in a reduction in the maximum temperature reached. The calculated results are in agreement with results from reverse-combustion experinments using samples of a tar sand. INTRODUCTION Reverse combustion is one thermal method of recovering hydrocarbons from porous underground forma-tions containing oil or tar.' In applying this method, air is introduced into the underground formation via an in-jection well. In one or more adjacent production wells, the mixture of air and hydrocarbons is ignited at the sand face. The combustion zone thus formed recedes toward the injection well, counter-current to the air flow (Fig. 1). Under certain conditions, the rate of recession of the combustion zone is sufficiently rapid that only a small fraction of the hydrocarbon at any point in the formation is consumed by combustion. If the combustion-zone temperature is sufficiently high, the uncon-sumed oil or tar in place may be partially distilled or cracked. This material then can flow as a vapor with the gaseous combustion products to the production well and subsequently be condensed at the surface. Under other conditions, the combustion-zone temperature may be so low that little, if any, of the hydrocarbon is vaporized. Nevertheless, the viscosity of the hydrocarbon may be reduced enough so that other recovery methods subsequently can be applied to produce oil at attractive rates. The maximum temperature achieved in the combustion zone and the velocity of movement are the two dependent variables defining the progress of the combustion zone. Presumably. knowledge of these factors will permit estimates to be made of oil recovery efficiency, oil and gas producticn rates and average amount of injection air required per barrel of oil recovered. The maximum temperature and combustion-zone vclocity are, in turn, expected to be dependent upon air flow rate, heat losses to surrounding formations, physical properties of the rock and the hydrocarbon. the extent to which the porous formation is saturated with the hydrocarbon, the rate of oxidation of the hydrocarbon and the amount of heat released. It is desirable that the relative importance of each of these factors be understood so that the results of laboratory tests of oil recovery by reverse combustion can be properly interpreted in terms of expected field performance. It is particularly desirable to assess the importance of heat lcsses because these are difficult to control or eliminate

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By E. A. Has, E. Mcl. Tittmann

Double roasting of sinter carrying a high percentage of lead concentrates, gave rise to the problem of removing the sheets of metallic lead formed in the wind boxes. The solution of the problem has been found in the water sealed wind boxes. The metallic lead is granulated and can be removed without seriously interfering with the operation of the machine and eliminates necessity of men going in wind boxes with air guns. THE practice of double sintering the charge for lead blast furnaces, which is now standard throughout the lead smelting industry, has introduced the rather difficult problem of cleaning the wind boxes on sintering machines used for the final pass. Two factors have more recently accentuated this problem: (1) the growing demand of workmen for better working conditions and less arduous labor, and (2) the growing dearth of crude lead ores and the improved grade of lead concentrates demand a charge carrying the maximum percentage of lead. One to 2 pct of such high lead charges (30 to 40) when processed on machines in reasonably good condition will pass through the grates and report in the wind boxes. One-half to three-quarters of this material will be metallic lead reduced by the coke breeze or other fuel mixed with the charge. This lead forms large cakes or chunks which are hard to remove and which substantially increase the time the machine is out of operation for cleaning the wind boxes. A high lead fall can reduce the operating time 30 pct. As a specific example, a 30 ft machine having 63 in. pallets, and equipped with three conventional wind boxes, requires 3 to 4 hr per day for removing the accumulation in the wind boxes when operated as a final pass machine. This same machine when operated on raw charge requires less than an hour per day for cleaning. To eliminate formation of large chunks of lead in the wind boxes of the final pass machines and time lost in cleaning the boxes, R. C. Rutherford of the Chihuahua smelter of the American Smelting and Refining Co., devised and patented* a wind box having a water bath to granulate the lead as it falls from the grate bars. Later, C. H. Harris of the San Luis plant made and patentedt an improvement on Rutherford's device in which the water bath seals the wind box in a manner permitting the latter to be readily cleaned without destroying the vacuum. The first machine to our knowledge to use the water bath box was at the Chihuahua plant along the lines of the Rutherford patent. In 1942, a machine was placed in operation at the El Paso plant which incorporated the features of both Rutherford and Harris. This machine is 40 ft long equipped with pallets 63 x 24 in., and having 4 wind boxes 10 ft 4 in. x 7 ft 2 in. x 51 ft 3 in. in size (fig. 1). The air from the fourth box is returned to the first three, and the gas from the first three discharged to a baghouse. The machine has conventional drive, discharge hopper,

Jan 1, 1951

By Louis Moyd

In the preparation of illustrations to accompany reports of investigations concerning particle shapes of various natural and manufactured materials proposed for use as he aggretates in concrete structures, it was found that stereoscopic views of such materials presented the information much more effectively than the usual two-dimensional photographs. With the whole-hearted cooperation of the Photographic Section, a technique was developed in the petro-graphic laboratory of the Concrete Research Division, U.S. Corps of Engineers, at Clinton, Miss., for simple and rapid preparation of paired stereoscopic photographs and micrographs. The method requires only equipment which is usually part of the general stock of any laboratory, and it is adaptable for all purposes in which three-dimensional views would be found superior to ordinary photographs. Stereoscopic Photographs Where the subject or subjects to be photographed are small but not of microscopic size, an ordinary camera having a ground-glass focusing screen is set up vertically over the field. The material to be photographed is placed on a card, the surface of which is suitable as a background. The card is mounted so that it can be tilted about 5' above and below the horizontal plane, on an axis that coincides with the north-south diameter of the viewing screen. A simple way of achieving this is to mount the card on an object having a convex lower surface. In our laboratory, a watch-glass has been used, with plasticene as the mounting medium. The convex surface should be mounted on a support having a round opening on top and a flat bottom. A roll of tape, a petri dish, a beaker, or any other piece of equipment having the proper shape to give stability to the setup will be satisfactory. The arrangement of the required equipment is shown in Fig 1. For the best results, the subject to be photographed should be mounted in the plane of the axis of rotation. To achieve this effect, the depth of the mass of plasticene between the background and the watch-glass is varied so that when the watch-glass is tilted back and forth on the axis, the subject to be photographed does not appear to move back and forth across the viewing screen. A permanent piece of equipment, embodying an adjustable vertical screw, with lock-nuts, could be made for this purpose. The subject may be illuminated in any manner desired. It was found that the presence of shadows intensifies the effect of depth. In taking the photographs, the concave surface is mounted so that one side of the background card is about 5' below the horizontal, while the axis remains in the horizontal plane. The subject is focused carefully on the ground glass and a picture is taken. The card is then tilted so that the opposite side is about 5' below the horizontal, while the axis still remains in the horizontal plane. The subject is again put in focus and another picture is taken. After both pictures are developed and printed, they are placed side by side in the same orientation and examined with a stereoscopic viewer. If depressions appear where there ought

Jan 1, 1950

By W. K. Hardy, H. H. Stadelmaier, L. J. Huetter

The ternary system Co-Sn-C was studied in the cobalt-rich region. The liquidus projection ulas established and two fonr -phase reactions were found. An isothermal section at 950°C was worked out. In the region studied the following phases were observed: cobalt-rich solid solution, graphite, binary compound y -cobalt-tin, and a ternary compound. As a result of the limited solubility of carbon in liquid cobalt-tin alloys, the investigation was limited to the cobalt-rich region. Tin contents up to 32 at. pct were studied. Cobalt of 99.99 pct purity, tin of 99.97 pct purity and synthetic graphite of 99.93 pct minimum purity prepare the alloys. Carbon determinations of all alloys were obtained by gas volumetric analysis. Samples were investigated microscopically and by X-ray diffraction using CoK, and FeK, radiation. Cooling curves were obtained with a number of alloys to determine the temperature of the four-phase reactions. The thermocouple was calibrated with the melting points of high-purity silver and copper. In the region studied the following phases were observed: Cobalt-rich solid solution (face-centered cubic) Graphite. Binary compound y (solidifies congruently at composition Cop~n)'. Ternary compound k which is face-centered cubic with superlattice and nonferromagnetic.' In Fig. 1 the fields representing the projections of the liquidus surfaces were determined by microscopic investigation and are labled by their primary phase. In the field labled C graphite is the primary phase. During solidification in this field much of the primary graphite was expelled through the surface of the melt. It could not always be established microscopically whether the remaining graphite was primary or purely eutectic. Therefore it was not possible to determine accurately the boundary curve which drops from the binary eutectic el at 1309 "~~ to the point of the four-phase reaction at F. The ter-nary carbide is the primary phase in the field labled k. To the right of this field the primary graphite is consistently nodular whereas flake graphite is observed at tin contents somewhat below F. The ternary carbide does not appear to solidify congruently. The graphite is attacked in a peritectic reaction along the boundary between k and C. Thus no graphite is observed in alloys in the k field. In alloys right of the boundary between k and C the graphite nodules are located in the center of the k crystallites, further documenting the peritectic nature of the reaction with the graphite. A four-phase reaction was found at F and 1120 &3"C. The most likely reaction is L+ CY-Co + C — k. Below the temperature of the binary eutectic ez at 1112" a second four-phase reaction was observed at E and 1100 lt3"C. It is the ternary eutectic L — CY-Co + k + y. Figs. 2(a ) to (e) show microstructures of the ternary alloys in the as-cast condition. Fig. 2(a) shows the eutectic a-Co + C (with some primary graphite) with the carbide k in the grain boundaries. Fig. 2(b) shows primary cobalt (dark areas) and the eutectic a-Co + k which is formed along F-E.

Jan 1, 1961

By W. H. Moore, E. T. Powell

IN the early days of mining in the Anthracite field, only the thicker and better seams of coal were mined, because of the limited mining and coal-cleaning facilities, therefore many of the thinner and less productive seams were permitted to remain unmined. With improvements in mining methods, the introduction of modem preparation plants, and the increased market demand for small-size coal, the thinner and more laminated seams have now become assets. In many instances these seams overlie the mined-out beds of the thicker and better seams, from which all recoverable coal was removed by the conventional breast-and-pillar method of mining. Some collieries in certain sections of the Anthracite field are now relying on these thinner and laminated seams. For the purpose of illustration, a large area in the Hickory Swamp-Ridge Basin of the western middle coal field has been selected, where as early as 1898 the No. 4, or Little Buck Mountain, seam was mined and pillars removed. The No. 5, or Buck Mountain, seam lying on a comparatively light pitch and with intervening strata of but 55 ft. of rock was not mined until 1935. Farther east, in the same basin the Nos. 8 and 9 seams, which are two splits of the Mammoth seam, have been mined and robbed and the workings have been abandoned since 1896. The overlying No. 9½ seam, or the upper split of the Mam- moth, and the No. 9¾ or 4-ft. seam remained virgin, with only an interval of 50 ft. of rock separating them, and with 40 to so ft. of rock strata separating the No. 9½ seam from the completely mined area of the Nos. 8 and 9 seams. These seams lie on a pitch of 45° on the south side of the basin and on 75° on the north side of the basin. Mining has been carried on in the 9½ and 9¾ seams for 3 years on both dips of the basin, for a distance of 3500 ft. In some sections the overlying strata of the thicker seams previously mined have settled without any apparent breaks in the upper strata, as indications have shown in the top split of the Mammoth; while in other areas the roof and bottom of this top split of the Mammoth have settled unevenly, thereby causing the bottom and roof to break into blocks. In attempting to mine over a large area of the No. 5 or Buck Mountain seam, a similar settlement has been encountered; the roof of the seam has been broken and a considerable amount of timbering has been necessary in order to make the mining of the seam possible. The conventional breast-and-pillar method, using shaker conveyors, has been used in the No. 5 seam, and a slant-breast method in the mining of Nos. 9½ and 9¾ seams. Mining OF Light-pitch Seams The No. 4 seam was mined and robbed by the conventional breast-and-pillar system. In this area the seam pitched from 5° to 25° on the north dip, averaged 8 ft. in thickness and had a slate bottom and a

Jan 1, 1942

By W. H. Moore, E. T. Powell

IN the early days of mining in the Anthracite field, only the thicker and better seams of coal were mined, because of the limited mining and coal-cleaning facilities, therefore many of the thinner and less productive seams were permitted to remain unmined. With improvements in mining methods, the introduction of modem preparation plants, and the increased market demand for small-size coal, the thinner and more laminated seams have now become assets. In many instances these seams overlie the mined-out beds of the thicker and better seams, from which all recoverable coal was removed by the conventional breast-and-pillar method of mining. Some collieries in certain sections of the Anthracite field are now relying on these thinner and laminated seams. For the purpose of illustration, a large area in the Hickory Swamp-Ridge Basin of the western middle coal field has been selected, where as early as 1898 the No. 4, or Little Buck Mountain, seam was mined and pillars removed. The No. 5, or Buck Mountain, seam lying on a comparatively light pitch and with intervening strata of but 55 ft. of rock was not mined until 1935. Farther east, in the same basin the Nos. 8 and 9 seams, which are two splits of the Mammoth seam, have been mined and robbed and the workings have been abandoned since 1896. The overlying No. 9½ seam, or the upper split of the Mam- moth, and the No. 9¾ or 4-ft. seam remained virgin, with only an interval of 50 ft. of rock separating them, and with 40 to so ft. of rock strata separating the No. 9½ seam from the completely mined area of the Nos. 8 and 9 seams. These seams lie on a pitch of 45° on the south side of the basin and on 75° on the north side of the basin. Mining has been carried on in the 9½ and 9¾ seams for 3 years on both dips of the basin, for a distance of 3500 ft. In some sections the overlying strata of the thicker seams previously mined have settled without any apparent breaks in the upper strata, as indications have shown in the top split of the Mammoth; while in other areas the roof and bottom of this top split of the Mammoth have settled unevenly, thereby causing the bottom and roof to break into blocks. In attempting to mine over a large area of the No. 5 or Buck Mountain seam, a similar settlement has been encountered; the roof of the seam has been broken and a considerable amount of timbering has been necessary in order to make the mining of the seam possible. The conventional breast-and-pillar method, using shaker conveyors, has been used in the No. 5 seam, and a slant-breast method in the mining of Nos. 9½ and 9¾ seams. Mining OF Light-pitch Seams The No. 4 seam was mined and robbed by the conventional breast-and-pillar system. In this area the seam pitched from 5° to 25° on the north dip, averaged 8 ft. in thickness and had a slate bottom and a

Jan 1, 1942

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas' have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968