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By Charles T. Malcomson

In the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segrega,ted and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promoters heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay. Several valuable contributions relating to coal briquetting are found in the Transactions. Charles Dorrance, Jr., has sketched briefly the history of the anthracite briquetting plants from the time of Loiseau's pioneer plant down to that of the Lehigh Coal & Navigation Co. at Lans-ford. Since then this phase of the industry has remained practically at

Jan 1, 1915

By A. E. J. Engel

INDUSTRIAL talcs and ground soapstones both include earth materials of different chemical and mineral compositions. In general, the industrial talcs are composed of silicates that contain appreciable amounts of magnesia. Generally talc, the mineral, is a predominant or at least common constituent. Talc, the mineral, is a hydrous magnesium silicate, with a suggested theoretical formula H2Mg3 (SiO3)4 or H2O.3MgO.4SiO2, which postulates 63.5 pct SiO2, 31.7 pct MgO, and 4.8 pct H20.11 Actually different single grains or leaves of pure talc have variations in water content ranging from 3.5 pct to more than 7 pct, as well as slight differences in the proportions of MgO and Si02.16 Only a very small percentage of the ground industrial talcs produced in the United States approaches the composition given above (see Table 1). The purer talcs invariably occur as alteration products of magnesium carbonate rocks. Some of these relatively pure talcs include compact, massive types largely mined in California, which are designated as steatite.38,58 In general, steatites cannot contain in excess of 1.5 pct CaO, 1.5 pct combined FeO and Fe203, and 4 pct A1203. The less pure varieties of massive talc and mixtures of magnesian silicates are commonly called soapstones, or merely talc. Many industrial earth products classified as talc or as soapstone contain a variety of minerals, especially serpentine (H4Mg,Si2O9), chlorites (hydrous magnesium, iron, aluminum silicates), tremolite (Ca2Mg5H2[SiO3]8), anthophyllite ([MgCa]SiO3), diopside (CaMg[SiO3]2), and quartz (SiO2). The carbonates calcite (CaC03), dolomite (CaMg[CO3]2), and magnesite (MgCO3) are also present in some industrial talcs and soapstones. Some of these minerals, as well as sulphides, sulphates, and iron and manganese oxides, if present at all or in excess of minute amounts, may alter the composition of the industrial talc sufficiently to restrict materially its use or to lower or destroy its value. These factors are discussed in a subsequent section of this chapter.

Jan 1, 1949

LATEST estimates of Russian steel production for 1951 give rise to the belief that on at least one vital front, the Western bloc of nations has maintained a definite advantage. On the surface, we are outproducing the Eastern bloc by more than twice. The United Nations Economic Commission for Europe estimates Russian output at 31.30 million tons, a 15 pct increase over the previous year. Production for the entire Iron Curtain is figured at 40.93 million tons. Western Europe alone produced 17 pct. more steel during the same period. The figures are misleading in one sense. We have no precise idea of how much steel is being used for arms. The Western nations are still expending much of their production for consumer goods, and you cant throw washing machines in a shooting war. It is significant to note that Russian production is well, beyond estimates made by world authorities prior to the current international situation. INTERIOR Secretary Oscar L. Chapman warns that the United States must make use of the resources of other nations or face mineral impoverishment once the time of struggle is over. He pointed out that the present struggle between two ideologies can leave the United States in such a state as to preclude anything but political' victory-with an accomp anying economic loss that will be irreparable. Chapman scored the attitude whereby conservation programs are looked upon as a luxury, pointing out that the nation faces an ever increasing need for action on that front. He also announced that the Bureau of Mines doubled its facilities for producing pure zirconium during 1950-51 at the request of the Atomic Energy Commission. Zirconium may be an important structural metal for atomic power devices. The Interior Secretary also said that the AEC has provided the Bureau with funds for the study of radioactive minerals and to help test and evaluate about 9000 ore samples believed to contain uranium.

Jan 1, 1952

By Albert Sauveur

This paper explains the possibility of using advantageously a boiling solution of sodium picrate to reveal dendritic segregation in steel. The mechanism of the action of the reagent is described. The failure of manganese alone to produce persistent dendritic segregation is also considered. IRON, like other metals, solidifies through the formation of dendritic crystals; iron alloys forming solid solutions, like other solid solutions, solidify likewise through the formation of dendritic crystals. The alloying elements or impurities as well as the inclusions segregate generally in the interstices, or "fillings," between the axes and branches of the dendrites; that is, in the portions last to solidify. This results in dendritic segregation or heterogeneity, which is generally persistent and makes possible the revelation of the dendritic crystallization of the metal through the selective action of a suitable etching reagent.1 For this purpose, a cupric solution, such as Le Chatelier's, is generally used, copper being deposited on the pure, or relatively pure, ferrite present in the axes while the fillings remain free, or relatively free., from copper deposition. The dendritic structure, formed on solidification in a steel containing 0.50 per cent. carbon, 0.37 per cent. manganese, 0.12 per cent. silicon, 0.07 per cent. sulfur, and 0.035 per cent. phosphorus is shown, after treatment with Le Chatelier reagent, in Fig. 1 under a magnification of 8 diameters. Commercial steel always contains inclusions of manganese sulfide, which are located in the fillings of the dendrites. Comstock has shown that boiling sodium picrate imparts a dark coloration to these inclusions. We find that this reagent likewise reveals dendritic segregations in commercial steel, as shown in Fig. 2, under a magnification of 8 diameters, which represents the same spot as that shown in Fig. 1. The fillings

Jan 2, 1924

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

[*E. O'C. Acker '86 Jinzoc Adachl '88 T. H. Aldrich '96 *Truman H. Aldrich '78 Walter H. Aldridge '89 *Anson W. Allen '87 John H. Allen '84 *Thomas Andrews '94 *William R. Analeby '90]

Jan 1, 1946

By J. H. Smith, H. W. Paxton

X HE recent investigation of Butler, McCabe, and paxton' on the vapor pressure of manganese gas in equilibrium with Mn-Fe alloys has been extended to include the iron-rich solutions and alloys in the two phase equilibrium region. The study of the phase equilibrium by Kurnakov and Troneva2 and the extensive reviews of the Mn-Fe system by Hansen,3 and Hellawe114 are not in agreement with regard to the location and extent of the equilibrium between the solid phases of fcc y and complex P in the temperature range above the eutectoid temperature of approximately 975Kwhere 0 decomposes to y and bcc a. An evaluation of the existing equilibrium data is confronted with the conflicting results presented by various investigators who used techniques requiring a quenching treatment to retain the high-temperature equilibrium or encountered temperature hysteresis during thermal analyses. The difficulty of suppressing the transformation of the manganese-rich concentrations of the y-solid solution during quenching has been well etablished.' To avoid this uncertainty the phase equilibrium was investigated at temperature by measuring the partial pressure of manganese gas in equilibrium

Jan 1, 1962

By H. E. Rorschach

Activity in Oklahoma fields declined in 1938 from the banner year of 1937. During the year, 1768 wells were completed as compared to 2632 completed during the year 1937. The following tabulation sets out details regarding the wells completed during the year: These computations do not take into account the wells drilled for repres-sure and salt-water disposal, and other nonexploratory wells. Purchasers' reports filed with the Corporation Commission of the State of Oklahoma show a total of 168,789,229 bbl. of oil purchased from Oklahoma leases in 1938, or a daily average of 462,436, a decrease of about 25 per cent from the year 1937. The outstanding operation of the year was the further development of the Ramsey pool, in western Payne County, the producing horizon being classified as the Wilcox. This pool was discovered on the last day in the year 1937, by the Mid-Continent Petroleum Corporation drilling on a unitized block in see. 18, T. 18 N., R. 2 E. The map in Fig. 1 shows the development at the end of the year 1938. An important discovery of the year was the Champlin Refining Company's No. 1 Boehm, in Garfield County, sec. 4-24N-8W., the producing horizon being the second Wilcox found at a depth of approximately 6700 ft. This pool was assigned the name of Hillsdale. Some of the offsets to this discovery well had not come up to expectations at the end of the year, but the discovery seems to be important as indicating that the Wilcox sand is productive in the Anadarko Basin area, providing that the right structural conditions are present.

Jan 1, 1939

By H. E. Rorschach

Activity in Oklahoma fields declined in 1938 from the banner year of 1937. During the year, 1768 wells were completed as compared to 2632 completed during the year 1937. The following tabulation sets out details regarding the wells completed during the year: These computations do not take into account the wells drilled for repres-sure and salt-water disposal, and other nonexploratory wells. Purchasers' reports filed with the Corporation Commission of the State of Oklahoma show a total of 168,789,229 bbl. of oil purchased from Oklahoma leases in 1938, or a daily average of 462,436, a decrease of about 25 per cent from the year 1937. The outstanding operation of the year was the further development of the Ramsey pool, in western Payne County, the producing horizon being classified as the Wilcox. This pool was discovered on the last day in the year 1937, by the Mid-Continent Petroleum Corporation drilling on a unitized block in see. 18, T. 18 N., R. 2 E. The map in Fig. 1 shows the development at the end of the year 1938. An important discovery of the year was the Champlin Refining Company's No. 1 Boehm, in Garfield County, sec. 4-24N-8W., the producing horizon being the second Wilcox found at a depth of approximately 6700 ft. This pool was assigned the name of Hillsdale. Some of the offsets to this discovery well had not come up to expectations at the end of the year, but the discovery seems to be important as indicating that the Wilcox sand is productive in the Anadarko Basin area, providing that the right structural conditions are present.

Jan 1, 1939

By H. J. Levinstein, H. J. Guggenheim

RbFeF3 is a transparent ferromagnet with a large faraday rotation which permits the direct observation of magnetic domain structures in bulk crystals. If the position of dislocations within the crystal were known a study of domain wall dislocation interactions would be possible. In this paper an etch pitting solution is described which gives a one-one correspondent between the etch pits and the dislocations intersecting the (100) surfaces of RbFeF3 crystals. In addition, RbFeF3 is shown to have sufficient plasticity so that known arrays of dislocaticms can be put into the crystal. It is concluded that RbFeF, is an ideal material for the investigation of domain wall dislocation interactions. THE influence of lattice defects on the motion of domain walls in ferromagnetic materials has been studied extensively both theoretically and experimentally.4 The experimental data obtained has been qualitative in nature due to the lack either of a quantitative knowledge of the magnetic domain array in the material or of the nature of the dislocation configuration in the material. At room temperature RbFeFJ has the cubic perovskite structure. It is ferromagnetic below 86°K.5,6 It is also transparent and has a large faraday rotation in the magnetic state.7 The domain structure of this material is observable in three dimensions in crystals which are millimeters in thickness.' Since RbFeF3 satisfies the requirements of having an easily visible three-dimensional magnetic domain structure, it was of interest to determine if the dislocation structure of the material could be determined and if the material was sufficiently plastic so that dislocations could be introduced into the as grown crystals. This is a report of the results of that investigation. EXPERIMENTAL PROCEDURE The crystals of RbFeFs used in this experiment were grown by a technique described elsewhere.5 In order to obtain flat strain-free surfaces, the samples were first cut to the crystal orientation desired and the surfaces were polished by employing standard metallographic techniques. The samples were then immersed in a solution of 1 to 3 g of KOH in 100 ml of water. This solution removes the damaged surface layers uniformly leaving a film on the surface of the sample. Etch pits are obtained by immersing the sample in an approximately 50-50 solution of 30 pct peroxide and concentrated acetic acid. The film formed during the KOH treatment turns deep red in color in the etching solution and flakes off the sample. The etching time required depends upon the pit size desired and

Jan 1, 1970

By W. H. Furlonge

WHILE fulfilling professional engagements, my travels over this portion of the Transvaal have been quite extensive—always on horseback however, so that anything like a thorough investigation of the ground passed over has been necessarily impossible; still, the more minute examination of certain small areas, coupled with general observations, has enabled me to form some idea as to the prominent geological features of the country as a whole. Anything like a complete or comprehensive description is indeed out of the question, as there are no proper maps of the country and the facilities for observation are limited. A large plateau, called the "High Veldt," stretches from east to west across the Transvaal. It is generally level, or gently rolling, and has an average elevation of 6000 feet above the sea; it is destitute of timber, and in fact greatly resembles the western prairies of North America. Rock-outcrops are not common in it. It terminates very abruptly to the east and northeast, the descent of 2000 or 3000 feet into the mountainous country that occupies its borders being made in a

Jan 1, 1890

By Frederic Becket

IN a recent article,1 which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investi-gations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the aus-tenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt construc-tively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford.2 Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of

Jan 1, 1934

By R. A. Swalin, A. H. Geisler

THIS study represents an investigation of the effect of annealing temperature on the texture of drawn molybdenum, iron, and an iron alloy containing 14 pct Al. The effect of temperature on annealing textures has not been widely investigated in the past. One of the obstacles in making such a study using usual X-ray diffraction techniques results from the

Jan 1, 1957

By E. A. Holbrook

Research, primarily, is finding out the truth. Research applied to enigeering opens the door to new principies and processes, the application of which benefits mankind in a material way. The engineer believes that investigation instituted with the primary view of making the results directly applicable to the industries is the highest type of research. Coal is essentially the basis of modern industrial civilization; therefore, any considerable research pertaining to coal must link itself to the industry by practical application of the results of the research. In other words, all investigational work connected in any way with coal leads to conclusions that permit a better understanding of the origin, nature of occurrence, composition, better and safer mining, more careful preparation, or greater efficiency in utilization of coal. Modern engineering research has been fostered essentially by universities and in the laboratories of institutions of learning. Coal problems that lend themselves to solution in the laboratories have been first attacked and are perhaps the farthest toward solution. For example, a great amount of research work has been carried out with the various phases of chemistry connected with coal. On the other hand, the equally important problems connected with methods of mining have received but little attention, primarily because their solution involves the continued use of a great and expensive laboratory, which is none other than the mine itself. As many of the problems already solved have had chemistry as their background, so many of the problems unsolved have physics as their background; there are also unsolved problems that deal in coal economics. Even psychology must be called upon in future coal-mining research as a basis for solving those great problems that deal with human relationships. 'In general, considerable advance has been made in coal research dealing with chemistry, not so much progress has been made with problems having physics and engineering as a background, while there is a tremendous range of untouched problems that deal essentially with business and psychology. Research in coal mining is not a new development. In the chronicles of the northern coal trade as published in the Transactions of the North

Jan 1, 1920

By James G. Crawford

Correlation Of water with its reservoir zone or formation has been one of the applications of oil-field water analysis of greatest direct value to the petroleum engineer. The water in each producing zone tends to have diagnostic characteristics by which it can be distinguished from every other water above or below that zone in that immediate vicinity. Representative analyses of oil-field waters from producing oil and gas fields in the Rocky Mountain region are included, and the diagnostic characteristics are discussed briefly. It is concluded that the generally dilute nature of Rocky Mountain oilfield waters is a result of dilution by meteoric waters, and that there is no relationship between presence or absence of commercial oil and the character of water in a structure. Introduction The study of waters associated With oil and gas began more than 50 years ago and has been well recognized by operators, engineers, and geologists for about 30 years. It appears unnecessary at this time to recite the history of oil-field water analysis; suffice to say that it has proved its worth many times to the production engineer suddenly confronted with water problems in producing oil and gas wells. Chemists and geologists have studied the possible origin of these waters and as Yet the subject is unsolved in many important phases. There are both local and regional problems connected with the explanation of concentrations and character- istics peculiar to each field, each subsurface zone and each province. Criteria useful in postulating the Occurrence of oil Or gas in One province completely fail when applied to another, and data carefully prepared and analyzed from one field may be actually misleading when applied to another. Correlation of water with its reservoir zone or formation has been one of the applications of oil-field water analysis of greatest direct value to the engineer. The concentrations and characteristics of the waters are essential to the engineers and geologists making interpretations of electric logs in this region. The behavior of water under conditions of reservoir temperature and pressure is dependent to a great degree upon its concentration and characteristics, and thus important to the reservoir engineer. With the advent of secondary recovery methods in the Rocky Mountain region the characteristics and treatment of water will become increasingly important. Premises upon which Correlation Is Based A brief review of the geochemical history of oil-field waters will suffice to present the premises upon which correlations of the waters are based. Sedimentary rocks which are now stratified were first sediments in seas, lakes and streams. These sediments were filled interstitially with connate water. With burial the sediments were compressed arid consolidated, integrated and indurated into bed rock and much of the connate water was dispelled. Following the formation of bed rock the strata were sub-

Jan 1, 1949

By Marvin Lee

Kansas continued holding, for its seventh year, the fourth position in the list of oil-producing states. The crude-oil production, according to purchaser's reports to the State Corporation Commission, was 40,008,940 bbl.; as assembled by the Oil and Gas Journal, 41,305,768, and by the U. S. Bureau of Mines, 41,942,000 barrels. Increase of production from 1932 was largely due to greater stability of the industry, and increased return of demand for Kansas oil, caused by the addition of Federal assistance in national production regulation which reduced illegal production, of some areas out of Kansas, that had been destructively competing with Kansas crude or its refined products, at less than cost of production. Prices continued to advance from the lowest level of 25c per barrel during part of May and June, until by the end of September 36" gravity crude had reached $1 per barrel and continued at this price the remainder of the year. Price stability, for a period greater than in previous years, has brought renewed confidence to those producing oil and has led to renewed interest and increased purchases of Kansas leases. Drilling was confined chiefly to the number of wells necessary to protect from offset and other drainage in the field and to meet the requirements of expiring lease contract deeper areas in Mid-Continent, are an added inducement to exploration. The renewal of interest in the search for new fields in Kansas is already apparent and 1934 will probably see more wildcatting than for several years. This is due both to the expiration of leases on large blocks and to actual demand of the industry for new fields. Exploration for favorable areas is being actively conducted by the various methods of surface, subsurface and core drilling and geophysical work. Much of western Kansas cannot be mapped by surface study and geophysical exploration has been of considerable assistance and has led to a large use of the seismograph. Several companies are conducting seismograph surveys and leasing on findings already secured. Development under the more favorable conditions of 1933 can be readily seen by the comparison of the following reports for the last weeks of December in the respective years.

Jan 1, 1934

BUFFALO C E Moyer, Chairman (Buffalo, N Y ) R M Jordan, Vice-Chairman H A Morlock, Secretary CHICAGO M E Nickel, Chairman (Chicago, Ill) A M Kroner, Vice-Chairman W R McLain, Secretary-Treasurer

Jan 1, 1960

PRESIDENT AND DIRECTOR HOWARD N. EAVENSON PITTSBURGH, PA PAST PRESIDENTS AND DIRECTORS SCOTT TURNER WASHINGTON, D. C. FREDERICK M BECKET NEW YORK, N. Y. VICE-PRESIDENT, TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y

Jan 1, 1935

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.' Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy's law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f'(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f'(S) can be calculated. It turns out that the experimentally derived f'(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942