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By Robert E. Bush, E. S. Mardock

The objective of this paper is to present practical methods of applying radioactivity logs to problems of interest both to those engaged in evaluating fundamental reservoir data as well as to those engaged in subsurface structural work. The basic theories underlying the operation of radioactivity logging methods are briefly discussed along with some of the problems arising in the interpretation of the log. Relative methods of quantitative interpretation are described, with a discussion of relative reference lines and specific examples are given showing the application of these relative quantitative interpretation methods. To show the variation of the methods described, specimen wells penetrating formations widely divergent in point of geologic age were selected to demonstrate the application. A relative reference line is determined for the Neutron Curve and by comparison to known petrophysical data such as porosities from diamond cores, a direct quantitative relationship is developed. The application of this relative calibration curve to logs of unknown wells will permit a reasonably accurate determination of porosity in limestone and dolomite formations. Specific examples are given showing the application of these relative methods of interpretation to logs of the Smackover limestone in Louisiana, the Edwards limestone and dolomites of South Texas, and Permian dolomites of West Texas. Radioactivity logs have been used extensively by the petroleum industry for a number of years and recognition of their value has grown steadily, not only as tools to aid in the solution of specific stratigraphic problems, but also as potential sources of the basic data necessary for the estimation of net pay and reserves. The value of radioactivity logs for stratigraphic work has been pointed out in the literature,1,2,4,5,6 and now has long been recognized by the industry, but the quantitative application of the logs has advanced but little beyond the stage of a strong conviction that radioactivity logging curves will some day provide the information on such important quantities as the porosity and the liquid saturation of the formations. During the past few years the staffs of the Lane-Wells Company and Well Surveys, Incorporated, have devoted a great deal of time, thought, and experimentation to the relationships existing between radioactivity curves and the lithologic conditions encountered, and this paper is, in a manner of' speaking, intended as a progress report of this work and includes suggestions which the authors have found useful in the interpretation of radioactivity logs. The section on theory is not intended as a complete exposition of the physical processes involved, but rather as a brief introduction to the reader of these processes so that he may acquire a better understanding of the behavior of the radioactivity curves under the varied conditions encountered in normal well logging. Three relative methods for using neutron logs for the quantitative estimation of porosity in limestone or dolomite are presented. These methods are based on the comparison of logs and porosity data from wells in Louisiana, South Texas, West Texas, and New Mexico. These areas were selected because not only were there more core data available from these areas but also the majority of these data were from limestone or dolomitic zones. The correlation between core data and logs is simpler for limestones and dolomites than it is for sandstones due to the fact that sandstones are more complex than limestones and differ more widely among themselves as to composition of cementing materials, siltiness, etc. When data applicable to the various types of sandstones are available, the authors hope to present a discussion similar to this paper covering sandstones or possibly a more general discussion covering all types of reservoir rocks. The relative methods for estimating porosity which are presented in this paper fall short of the absolute method sought. However, these methods possess the advantage that they can be applied to almost any neutron log as long as the range of application is held within the limits imposed by the local lithologic conditions which prevailed during calibration, i.e., these methods are for short range application only. THE THEORETICAL BASIS FOR RADIOACTIVITY LOGGING The two redioactivity logging curves commercially available today are the

Jan 1, 1950

By Craig S. Hartley

An approximate expression is obtained for the energy of a closed dislocation loop in equi1ibriu)n with a constant net stress. The result obtained is valid for loops in isotropic or anisotropzc materials provided that they are suJficiently large that the energy per unit length of a segment of the loop can be approximated by that of an infinite straight dislocation tangent to the loop. It is shown that this approximation leads to very close agreement with a more rigorous calculation of the elastic energy of a circular glide loop. The Gibbs-Wulff Form, GWF, of a dislocation is the closed planar loop which has the smallest elastic self-energy of all possible loops having the same Burgers vector and enclosing a fixed area, A.' The energy of such a loop is related to the net resolved shear stress* required to expand the loop and to the stress required to activate a Frank-Read source.223 In the following sectiorls the problem of determining the form of the GWF is discussed and an approximate method for calculating its elastic self-energy is presented. It is demonstrated that the approximations employed lead to no serious errors when applied to a calculation of the elastic energy of a circular glide loop. This method is then used to obtain a closed form expression for the energy of GWFs in isotropic and anisotropic materials. THEORY Burton, Frank, and cabrera4 have proved that the relationship of the equilibrium shape of a two-dimensional array of atoms under the influence of the Gibbs free energy associated with unit length of its boundary, G(O), is that the polar plot of G(0) vs 0 is proportional to the pedal of the GWF.* The angle 0 is measured "The pedal of the polar graph ofG(0) vs0 is the envelope of tangents to the eraph.relative to some crystallographic reference direction. The difficulty in applying this result to a closed dislocation loop arises from the self-interaction of the loop. For a dislocation the energy analogous to G(0) is a function of the total configurati~n.~ Consequently the relation which determines the GWF is an integro-differential equation rather than the simple differen- tial equation which results when G(8) is a function of 0 alone. Mitchell and smialek3 and Brown~ have used the self-stress concept introduced by ~rown' to calculate the shapes of dislocations in equilibrium with an applied stress. In this approach the glide force on an element of the dislocation loop due to the interaction of the element with the rest of the loop is equated to the glide force exerted by the local applied stress. The shape of the loop is then adjusted so that the two forces above are equal at all points on the loop. It is possible to calculate the energies of such loops by noting that, for equilibrium with an applied stress, the energy is equal to pijbiAj (summation convention) where bi is the Burgers vector, p.. is the local net stress tensor, and Ai is a vector directed perpendicular to the plane of thd loop with magnitude equal to the area of the loop. Also Brown' has calculated the energy of a hypothetical polygonal GWF using the above technique and anisotropic elasticity. However, his indicated solution for the energy in the general case of an arbitrary GWF is only slightly less involved than an iterative solution of the integrodifferential equation referred to earlier. In the present work the approximation employed by DeWit and Koehler' is used to calculate the energy of a closed loop in equilibrium with an applied stress. That is, the energy of a loop segment, ds, is approximated by the product of ds and the energy per unit length of an infinite, straight dislocation in a cylinder coaxial with the tangent to the loop at the angular position of the segment. This is known as the "line tension" approximation. The inner cutoff radius of the elastic solution defines the core radius, while the outer cutoff radius is determined by some characteristic dimension of the loop. Actually, both of these radii vary with the edge-screw character of the segment. The effective core radius changes because of the orientation dependence of the Peierls width of a dislocation,8 and the outer radius should be the radial distance from the circumference of the loop to the center of symmetry of the area enclosed by the loop.g However, since the energy varies logarithmically with the ratio of these radii while depending directly on the effective elastic constants, only the effect of the latter is considered. This approximation also neglects the self-interaction of the loop segments. For small loops this will doubtless be extremely important, but for large glide loops produced by plastic deformation the self-interaction is not nearly so important in determining the energy of the loop. This point is illustrated by the following calculation of the energy of a circular loop. Consider a circular loop of radius R which lies in the XI - x, plane of an infinite isotropic continuum and whose Burgers vector makes an angle $ with xs. The first-order solution for the elastic self-energy is:'

Jan 1, 1970

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR's are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR's in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By O. W. Ellis

CERTAIN alloys1 that, as a result of quenching, are retained in the form of homogeneous solid solution are known to increase in hardness and strength on standing at room temperature or on heating at slightly elevated temperatures. Other alloys" that, on rapid cooling, are held in the form of homogeneous solid solution (as, for example, certain steels) behave in like manner on heating to somewhat higher temperatures. The observed increase in the hardness and strength of these alloys, referred to as "aging" or as "secondary hardness," is widely accepted as being occasioned, either in whole or in part, by the precipitation in submicroscopic form of such constituents as were held in supersaturated solid solution as a result of cooling in excess of a certain critical rate. In earlier discussions of the cause of age hardening or secondary hardness, the question of the hardness of the precipitated particles does not appear to have been raised. At present, however, the general opinion appears to be that age hardening and secondary hardness are occasioned by the precipitation of hard particles within the supersaturated solid substance.3 The authors may be wrong in their belief that the last is a prevailing opinion. Nevertheless, it is thought that the following experiments,

Jan 7, 1924

By R. W. Raymond

EDWARD COOPER, was born in New York City, October 26, 1824. His father, Peter Cooper, to say nothing of manifold reasons for fame as an inventor and philanthropist, deserves to be remembered as a pioneer in the establishment of public schools; and it is not surprising that he sent his son to one of the democratic institutions in which he was himself so ardently interested. From the public school Edward Cooper went to Columbia. College, where he made the acquaintance of Abram S. Hewitt, who was first his tutor, afterwards his traveling companion, brother-in-law, business partner and life-long friend.* For twenty years I was the consulting engineer of the firm of Cooper & Hewitt, and also connected with the work of the Cooper Union, in which they were both deeply interested and faithfully active. On the basis of the intimate knowledge thus gained, I venture an estimate of Edward Cooper's character and career which, if not fully comprehensive, may facilitate a juster estimate than would be reached by the strident of those data which the modesty of the man permitted to be placed upon public record. Edward Cooper's mind was one of the most active, accurate and subtle with which I have ever come into contact: He had inherited from his father a sunny, benevolent temperament, and' the irresistible impulse to attack all new problems which challenged his attention. His thorough education had 'indeed made him wiser than his father, both in philanthropy and in technical inventions. He could condemn and reject a proposition which Peter Cooper would have embraced, in a splendid, though ignorant, faith that nothing was impossible to an. American, and that the word ? impossible " was simply a label,

Jul 1, 1906

By Alan Kissock

MOLYBDENUM is thought of as one of the rarer elements, for though it occurs in almost every country of the world it is seldom found in commercial quantities. In this country, however, there is one deposit which makes the term "rare" a misnomer. There are two commercially mined molybdenum minerals: molybdenite, the sulfide, and wulfenite, a lead molybdate. Of these two only the former is of any con- sequence but wulfenite is of mineralogical interest. It is frequently associated with oxidized lead ores and particularly in arid sections. Deposits, however, are usually quite superficial. It is highly oxidized and yet it does not appear to be an alteration product for it apparently disappears below water level and I know of no case where primary molybdenite, or in fact any molybdenum whatever has been identified below these surface wulfenite occurrences. The genesis of wulfenite would make an !- interesting study.

Jan 1, 1933

Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribution to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While' it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind maybe said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others. In a generic way, metallurgists now speak of carbides, sub-carbides, double carbides, special carbides, and other combinations. It is very desirable that these should be accurately defined and understood. It is also desirable to know whether there are other or new forms; if so, can these be separated and their characteristics obtained. It may be interesting to point out that the carbon compounds now definitely known are stated to number over 80,000. It is very probable, therefore, that there is room for much valuable and useful research to be carried out with the object of increasing our knowledge of the various combinations of carbon with iron, as probably some of these are still unknown

Jan 5, 1914

By Charles R. Austin, Carl H. Samans

In an earlier serics of studies on 18-8 stainless steel at 600º, 700º, and 800ºC.l one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manufactured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in. dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0.07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recommended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 75Q°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8-in. dia., air cooling followed the annealing treatment. These treatments permitted two direct comparisons: (1) between the 1150" and 950°C. treatments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950" and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By Carl H. Samans, Charles R. Austin

In an earlier serics of studies on 18-8 stainless steel at 600º, 700º, and 800ºC.l one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manufactured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in. dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0.07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recommended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 75Q°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8-in. dia., air cooling followed the annealing treatment. These treatments permitted two direct comparisons: (1) between the 1150" and 950°C. treatments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950" and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By H. M. St. John

Like every present-day manufacturer, the brass foundryman is faced with the necessity of reducing the cost of his finished product without impairing its appearance or quality. He must use every economy that the progress of art and science puts at his disposal and should also be alert to profit by any peculiarity in his own situation or the nature of his product that may give him an exceptional advantage. Much can be accomplished by the adoption of labor-saving equipment and improved methods of melting, molding and handling. Control of pouring temperature, study of defective castings and their causes, laboratory control of molding sand and core mixtures, the use of less expensive alloys, all contribute to the desired end. Assuming that the composition of the alloy is already as inexpensive as the character of the casting will permit, still further savings can be made by the intelligent purchase and utilization of the metals needed to produce the desired analysis. Functions of Secondary and Virgin Metals in Casting Brass It is no longer a general assumption among foundrymen that quality castings must be made from an "all virgin" mix. If suitable secondary metals can be obtained more cheaply it is wasteful to use any larger proportion of virgin metal than is required to produce castings of the desired properties. To follow such a course, however, imposes upon the foundryman a heavier obligation than was formerly the case, to make sure by test and inspection that his castings really are of the desired quality. So long as he used the most expensive grades of metal and his melting practice was reasonably correct he was not obliged to give much thought to the quality of the metal in the castings. If he is to use secondary metals he must, in order to retain the confidence of his customer, examine these metals very carefully before use, exercise scrupulous control over his melting and pouring conditions and examine his castings closely. These statements apply more particularly to the jobbing foundry. The foundry department in a manufacturing plant is in a somewhat

Jan 1, 1930

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By L. H. DeWald

During the examination of various commercial brands of copper wire bars, which had exhibited different degrees of adaptability for being drawn into fine gages of wire by the present-day high speed machine, it was found that each brand had a more or less characteristic crystal macrostructure. The extremes of these macrostructures are similar FIG. 1.-EFFECT OF METAL TEMPERATURE IN CASTING ON CRYSTAL MACROSTRUCTURE OF BAR. Reading from left to right, metal temperatures were 1166" C., 1149" C., 1132" C.. 1121" C., 1093" C. to the maximum variation shown in the photomacrographs reproduced in Fig. 1. As the various brands did not differ materially in chemical composition, it was concluded that the differences in structure were the result of variations in casting technique.

Jan 1, 1931

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By William H. Emmons

Discussion of the paper of William H. Emmons, presented at the Canal Zone meeting, November, 1910, and printed in Bulletin No. 46, October, 1910, pp. 767 to S37. CHARLES R,. KEYES, Des Moines, Ia. (communication to the Secretary*) :-It is not in a spirit of criticism that I offer a supplemental suggestion or two on the subjects covered by this valuable and highly instructive memoir. There are two points which, in my opinion, should have received greater emphasis in Mr. Emmons's excellent paper. One is the fundamental role played by the chlorides under certain conditions in ore-formation. The other is the possible establishment of geographic relationships among the four phenomena of (1) excessive chloridic content of mine-waters; (2) the abundance of chloridic compounds of the precious metals ; (3) the presence of. manganese oxides; and (4) the diminishing importance, in ore-genesis, of the metallic sulphates. Although Mr. Emmons's notes refer to gold alone, it may be pertinently asked whether the same principles do not hold good for silver and copper also, since these metals form, together with gold, a distinct and well-known chemical group. That the reactions involved apply equally well to the other two metals mentioned, is shown by a number of recent observations and discussions. Chloridic ores of silver are, as I have lately endeavored to show, mainly worked in. arid or desert regions only ; and the great deposits of disseminated copper-ores are similarly characteristic of such regions, in which both classes doubtless owe their formation to the abundance of saline materials derived from desert dusts, and to the .plentiful and almost universal presence of manganese oxide. Under these climatic conditions, silver is somewhat more abundantly deposited than copper and gold, because its chloride is so much * Received Nov. 11, 1910.

Jun 1, 1911

By James R. Cudworth, Joseph C. Mead

The Birmingham district of Alabama has utilized the slag from its blast furnaces consistently since the earliest development of the slag industry. Today there are producers of slag cement who started business in 1900, and who have, under a progressive policy, expanded the number of their products to meet present demands. There are producers of slag aggregates and other crushed slag products who have been successful for periods of over thirty years. There are at the present two companies, Cheney Lime and Cement Co. and the Southern Cement Co., manufacturing puzzolan cement; two companies, Birmingham Slag Co. and Woodstock Slag Co., making slag aggregates and by-products; one company, Tennessee Coal, Iron and Railway Co., a subsidiary of the U. S. Steel Corporation, producing ground open-hearth basic slag for soil conditioning. Two companies, the Sloss Sheffield Steel and Iron Co. and the Woodstock Slag Co., make slag concrete in ready-mix plants and one company, the Superock Company, manufactures fine and coarse slag aggregates under a new granulation process. NO Portland cement is made with slag as an ingredient, because dolomite is used so extensively as a blast-furnace flux that the magnesium content of the slag is excessive. Sources of Slag In the Birmingham district there are 22 blast furnaces, of which the majority are in blast. The present production is 165,000 tons of pig iron monthly; the production in 1935 was 1,297,960 gross tons1. There arc also two blast furnaces at Gadsden and one ferroalloy electric furnaee at Anniston. From these two sources is obtained slag to approximately 1.1 tons per ton of pig iron. History of Development of the Industry The history of the local utilization of slag as an industry probably starts with the Birmingharii Slag Cement Co. This company was

Jan 1, 1938

By Joseph C. Mead, James R. Cudworth

The Birmingham district of Alabama has utilized the slag from its blast furnaces consistently since the earliest development of the slag industry. Today there are producers of slag cement who started business in 1900, and who have, under a progressive policy, expanded the number of their products to meet present demands. There are producers of slag aggregates and other crushed slag products who have been successful for periods of over thirty years. There are at the present two companies, Cheney Lime and Cement Co. and the Southern Cement Co., manufacturing puzzolan cement; two companies, Birmingham Slag Co. and Woodstock Slag Co., making slag aggregates and by-products; one company, Tennessee Coal, Iron and Railway Co., a subsidiary of the U. S. Steel Corporation, producing ground open-hearth basic slag for soil conditioning. Two companies, the Sloss Sheffield Steel and Iron Co. and the Woodstock Slag Co., make slag concrete in ready-mix plants and one company, the Superock Company, manufactures fine and coarse slag aggregates under a new granulation process. NO Portland cement is made with slag as an ingredient, because dolomite is used so extensively as a blast-furnace flux that the magnesium content of the slag is excessive. Sources of Slag In the Birmingham district there are 22 blast furnaces, of which the majority are in blast. The present production is 165,000 tons of pig iron monthly; the production in 1935 was 1,297,960 gross tons1. There arc also two blast furnaces at Gadsden and one ferroalloy electric furnaee at Anniston. From these two sources is obtained slag to approximately 1.1 tons per ton of pig iron. History of Development of the Industry The history of the local utilization of slag as an industry probably starts with the Birmingharii Slag Cement Co. This company was

Jan 1, 1938

By P. van Meurs

This paper describes a technique which permits visual observation of oil displacement processes througlrout the interior of a porous structure as thick as 2 in. A model having glass walls is filled with finely powdered glass. Such a model becomes completely transparent if the powdered glass pack is saturated with an oil having the same refractive index as the glass. When water or gar, with a refractive index different from that of the oil (glass) is injected, the model becomes opaque in the space occupied by the water (gar). visual observation and photography of these displacement processes are thus rendered possible. The following processes have been studied: (I) displacement of oil by water (linear drive) in a homo-geneous formation and in a stratified formation, (2) water flooding (five-spot well pattern), (3) solution gas-drive process, and (4) oil-bank formation. INTRODUCTION Most of the scaled model experiments heretofore carried out in the Koninklijke/Shell Laboratorium, Amsterdam, have been done in steel containers, in which oil-saturated sand packs represented the oil-bearing formation. In such experiments, for instance those on the displacement of oil by water, the cumulative oil production was measured as a function of the cumulative water injection. In order to interpret the measured production data, a need has for some time been felt for a means of observing visually what happens in the course of such experiments. Some information of this kind was obtained earlier by observing the water-oil distribution in various cross sections of the sand after the conclusion of the experiment.' However, the technique used did not guarantee that the fluid distribution remained undisturbed. Moreover, the procedure was somewhat elaborate and the information obtained limited. Therefore a new technique has been developed, which is described below. DESCRIPTION OF EXPERIMENTAL TECHNIQUE AND APPARATUS Glass models simulating part of an oil reservoir are filled with ground Pyrex glass of a specific grain size, representing the porous structure of the prototype. Before an experiment is started, the porous formation has to be saturated completely with an oil having exactly the same refractive index as the Pyrex glass powder. All light-scattering surfaces of the glass grains become invisible and the formation is then transparent. If the oil is displaced by another fluid (e.g. by water in a water-drive experiment, or by gas liberated from the oil in a solution gas-drive experiment) the formation becomes opaque in the region where the oil is expelled from the rock.* The back of the apparatus is painted black and illumination is from the front; therefore, in the photographs of the experiments, the oil-bearing formation appears black, whereas the water- or gas-invaded areas are white.

Jan 1, 1958

By R. P. Smith

The carbon content of a number of alloys ranging (before carburitation) from purified iron to purified cobalt was determined for fixed activities of carbon by equilibration with each of six CO-CO2 atmosphere at 1000°C. At fixed carbon activity, the carbon content decreases continuously with increasing cobalt content. For concentrations of 0 to 50 at. pct Co the results can be expressed by a linear interaction equation of the type In y2 = 7.76n2/(n1+n3)+ 2.30 n3/(n1+n3) where y2 is the activity coefficient of carbon (standard state such that y2— 1 as n2 — 0 in the Fe-C binary) and n1, n2, and n3 are the number of atoms of iron, carbon, and cobalt per unit weight of alloy. The results are also given in terms of the a functions. In the same concentration range, the results are in accord with the regular solution theory of Alcock and Richardson. THE carbon content of Fe-Si, Fe-Mn, and Fe-Ni alloys at fixed activities of carbon has been reported previously.'-, The present work extends R. P. SMITH, Member AIME, is Research Chemist, E. C. Bain Laboratory for Fundamental Research, United States Steel Corp., Research Center, Monroeville, Pa. these measurements to a series of Fe-Co alloys. These alloys, like the Fe-Ni alloys, are fcc ("aus-tenitic") over the entire range of composition at 1000°C. EXPERIMENTAL PROCEDURE The alloys were made from electrolytic cobalt and Plast-Iron in a small vacuum-melting furnace. A small amount of graphite was added to each melt to keep the oxygen content low. The ingots were analyzed for iron and carbon: the amount of cobalt was obtained by difference. Analysis of the top and bottom of the ingots indicated that they were uniform in alloy content. Except for the pure cobalt the ingots were hot-rolled to approximately 0.15 cm thickness, cleaned by sandblasting, then cold-rolled to about 0.045 cm. We were not successful in cold rolling the pure cobalt; therefore it was hot-rolled to the final thickness. The last traces of surface oxide were removed by acid pickel, then the samples were treated in a hydrogen-2 pct water vapor mixture at 1100°C to remove carbon and most of the oxygen. The carburizing procedure was similar to that previously described.1,2,4 The alloys in the form of strips about 1.7 cm wide, 7.5 cm long, and 0.04 cm thick, together with a similar specimen of purified iron, were equilibrated with each of six CO-CO2 mixtures of fixed composition, then quenched in the

Jan 1, 1965

By P. C. Hodges

WHILE there is very little romance connected with the operation of a stone quarry, yet to those who have participated in the growth and development of a business that has been a pioneer in its field and that FIG. 1.-LOCATION OF PROPERTY OF MARBLE CLIFF QUARRIES COMPANY. has been in continual operation two-thirds of a century there is bound to be a background of experience, which if properly capitalized, brings progress as well as satisfaction in its accomplishment.

Jan 1, 1936

By J. W. Whalen

The design, operation and evaluation of an instrumental method for the determination of fluid saturation in porous materials during multiphase flow studies is described. The presence of a magnetic tracer comprising approximately 20 per cent by weight of the aqueous phase is necessary in the utilization of this method. The results of two-phase relative permeability studies on two samples of porous media are presented. The realizable accuracy of the magnetic susceptibility apparatus in fluid saturation determination is estimated to be 2 saturation per cent. The response characteristics of the instrument, together with its simplicity of operation and maintenance are sufficient to recommend its use in routine laboratory studies. INTRODUCTION The problem of fluid saturation determination in laboratory multiphase flow studies characterizing oil recovery processes is one which has been given exhaustive study. Briefly the requirements which are considered essential for a method sewing this purpose are: (1) that the measurement be made external to the porous rock sample under study with no interruption of the fluid flow pattern, (2) the saturation indication must be independent of fluid distribution in the volume scanned by the measuring device, (3) the sensing element should have a small field of definition enabling several independent measurements to be made along the length of a core sample, and (4) the properties of the fluid phases should not be too greatly influenced by required tracer substances. Several methods of saturation determination have found acceptance as meeting most of the above requirements. These include resistivity,1 X-Ray absorption,2,3,4 radiotracers,5,6,7 and neutron8 diffraction The merits of these techniques have been discussed elsewhere in detail and will not be considered here. It may, however. be pointed out that the elaborate instrumentation required by the methods mentioned above, with the exception of the resistivity method (which is undesirable from other standpoints) encourages the development of methods of saturation determination which, while meeting the requirements listed, are simple to operate and maintain. It is the purpose of this paper to describe the instrumentation and evaluation of a technique for the determination of fluid saturation which combines relative simplicity with an accuracy and applicability comparable with methods now in practice. DESCRIPTION OF THE METHOD If the magnetic susceptibility of one of the fluid phases contained within a porous material is sufficiently greater than that of the remaining phases, the fluid content of the material with respect to that phase may be determined by an induction measurement. This may be accomplished by measuring the induced voltage in the secondary of a transformer which contains the porous sample and its interstitial fluids as a portion of the magnetic flux path. Since the fluids used in multiphase flow studies involving petroleum reservoir samples possess uniformly low magnetic susceptibilities, the use of a magnetic tracer in one of the fluid phases is required. In view of the relatively high paramagnetic susceptibility of salts of the transition elements, together with their high water solubility. these compounds become logical choices as tracer materials. Cobaltous chloride, having a specific magnetic susceptibility of 17.5 x 106 cgs electromagnetic units, was used as the tracer material throughout this work, in a concentration of approximately 20 per cent by weight in the aqueous phase. MAGNETIC SUSCEPTIBILITY APPARATUS Basically, the magnetic susceptibility apparatus consists of a transformer serving as the detecting head, a

Jan 1, 1955