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By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.' The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.' Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others' found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer' found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By Louis J. Demer, Paul A. Beck

As reported in a previous publication,1 isothermal grain growth in high purity aluminum and in an aluminum alloy with 2 pct magnesium can be adequately described by means of the empirical relation: [ ] or in some cases, by the simpler relation, [ ] Here, D is the average grain size after an annealing period t. The annealing period includes the time for complete recrystallization R, and the time for grain growth [to]. DA is the grain size as recrystallized, n is a parameter depending on the temperature and on the material. The effect of 2 pct magnesium in solid solution was to decrease D, and to increase R, A and n at a given temperature. The present work was undertaken in order to investigate the above listed effects of magnesium in solid solution, as functions of the magnesium content. The work also includes the study of certain anomalous effects observed in the recrystallization and grain growth of the 2 pct magnesium alloy at 350°C. EXPERIMENTAL PROCEDURE The method of producing the ingots used in this work was described in detail1 and need not be reproduced here. The materials used were high purity aluminum, furnished by the Aluminum Co. of America, of lot analysis shown in Table I and magnesium from a high purity distilled stock of magnesium crystals. [ ] Ingots were prepared for a series of binary aluminum-magnesium alloys of increasing alloy content. The numbers used to designate these ingots and their magnesium contents by chemical analysis are given in Table 2. [ ] The analyses showed no difference in composition between the top and the bottom of the ingots. Spectrographic analysis of the ingots for elements other than magnesium showed, within the limits of accuracy of the method, no increase in impurities over the amounts given in the lot analysis for the high purity aluminum in Table I. Careful microscopic study of ingot 21 in the as-cast condition, at magnifications up t0 1500X, revealed a cer-

Jan 1, 1948

William H. Blauvelt, Syracuse, N. Y.:—Is the coal itself from which the briquettes are made of good quality for steam-ing-purposes? Mr. Parker :—It is an anthracite coal mined near Bank-head arid used on the Canadian Pacific railroad. It contains about 83 of carbon, 8 of ash, and 8 per cent. of volatile material. With regard to briquetting of a mixture of fine coal and coke-dust, I understand that a plant has been installed near Detroit in which coke is mixed with anthracite; also the plant of the United Gas Improvement Co. near Philadelphia is briquetting a mixture of anthracite coal, the resultant briquettes being used in the gas-retorts. Mr. Blauvelt:—The purpose of the Detroit briquette-plant of the Solvay Process Co. has been partly to use up the coke-breeze from the by-product ovens and partly to utilize the pitch. There is no necessity for mixing anthracite with the coke-breeze, but the supply of breeze is limited, and anthracite

Jan 1, 1909

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.' These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,' one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z' alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By J. Nutting, J. W. Cahn

WITH the development of thin film techniques for the direct examination of metals in the electron microscope some new problems in quantitative metallography have become apparent. In order to obtain certain contrast effects in the electron optical image when examining thin films from alloys containing dispersed phases, it is essential to use films of a thickness at least two or three times greater than that of the mean particle diameter of the dispersed phase. From micrographs of such specimens it may be desired to obtain the volume fraction of the dispersed phase and the number of particles of the phase in a unit volume of the matrix. Under these conditions the particles sectioned by

Jan 1, 1960

By D. J. McAdam

In 1917 Haighl presented evidence that under simultaneous corrosion and cyclic stress metals may fail at lower stresses than if the corrosion is prior to the cyclic stress. In 1926 the author, while investigating the cooling effect of water on the fatigue resistance of metals, found that under these conditions steel specimens fail at stresses far below the endurance limit.2 (By "endurance limit" is here meant the fatigue limit obtained with specimens as free as possible from stress concentration and corrosive influences.) This led to an investigation (at the Naval Engineering Experiment Station, Annapolis, Md.) of the influence of cyclic stress on corrosion. This investigation may be divided into three parts. The first part was a general survey of the conditions necessary to cause complete failure under corrosion and cyclic stress of relatively high frequency. The entire process by which metals fail under these conditions was called LLcorrosion-fatigue." Corrosion-fatigue limits" for a large number of metals were determined and the relationships of these limits to chemical composition, heat treatment and physical properties were established. The conclusion was reached that corrosion-fatigue is due to the accelerating influence of cyclic stress on corrosion. Results of this part of the investigation were presented in five papers.*-= The second part of the investigation was a preliminary study of the influence of cyclic stress on corrosion. Each experiment was conducted in two stages. The first was a corrosion stage in which the specimen was corroded under cyclic stress; the second was a fatigue stage, in which the previously corroded specimen was tested (without further corrosion) to determine its fatigue limit. The difference between this fatigue limit and the endurance limit was used as a criterion of the "damage" due to

Jan 1, 1932

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By C. A. Heiland

The following summary is written for the benefit of the practical operator in the nonmetallic field who wishes to know what geophysics has done and may be expected to do in his line of work. His problem is quite different from that of the geophysicist who has operated with various or all methods and has followed the literature, and who is assumed to be familiar with the geologic possibilities and limitations of each method. This article is not written for the latter, although he may be interested in the four or five hitherto unpublished surveys described. To the operator, on the other hand, geophysics is only secondary. His problem is to determine which geophysical method is best suited to his special needs. If he wanted to know, however, which method could be used to locate a certain material of given physical properties, building stone, for instance, he would have to wade through a tremendous amount of geophysical literature, bibliographies and articles, before he could find what he wanted. Therefore, the purpose of this summary is to present the geological problems first and then to discuss the comparative merits of the geophysical methods that can be, or have been, applied. Choice of Geophysical Methods in Oil, Civil and Mining Engineering In the first two of these fields, the geological problems are not nearly so complex as in the metal and nonmetallic mining fields. The selection of the correct geophysical method in these fields is not nearly so difficult for the operator. For oil prospecting, his problems have been discussed exhaustively by E. DeGolyer.(1) † In civil engineering (foundation and ground-water work), the usefulness of electrical methods has been so well established that there is hardly any choice of other methods at present. The situation may be changed in the future with the perfection of the seismic reflection method for shallow depths. In the mining field the operator and often the geophysicist himself finds difficulty in determining which method is best suited for a given

Jan 1, 1934

By J. L. Christie, W. R. Webster, R. S. Pratt

Since the delivery of our paper on Some Comparative Properties of Tough-pitch and Phosphorized Copper,1 a new brand known as "oxygen-free high-conductivity copper" (brand OFHC) has become available to consumers. It was thought desirable to make a comparison between the properties of this material and those of the materials covered by our original paper and its discussion. Preliminary tests had indicated some notable differences. A billet of oxygen-free high-conductivity copper was taken from regular production. A chemical analysis of the particular billet was not made, but the producer of the material has given as typical the analysis shown in Table 1. The

Jan 1, 1933

By S. J. Green, R. D. Perkins

Little data exists on the high strain rate behavior of geologic materials. Uniaxial stress tests by Kumar1 and by Serdengecti and Boozer2 present some results to strain rates in the range 10 to 103 per sec. The two references cited are the only ones the authors found for high strain rates. Techniques for experiments at high strain rates are not well developed and, in general, leave questions with respect to interpretation of data when the material behaves in a brittle manner. The most reliable data at very high strain rates (104 to 106 per sec) are found in some recent flat-plate work3-5 where experimenters have impacted one plate into another, thereby creating a uniaxial strain loading. The standard uniaxial stress-strain curves cannot be obtained directly from these tests; however, yield (or fracture) may be studied by measuring the "elastic" wave magnitude. These data then may be compared to uniaxial stress data by resorting to some preassumed yield/fracture criteria. Even with the most liberal interpretation of existing data, little can be said of the effects of high strain rate on stiffness, yield/fracture, and post-fracture behavior of geologic materials. It is the purpose of this work to begin to add to the understanding. The data presented here are intended to provide material information for use in calculating the response of geologic materials to high rate deformations. These data can be applied directly to determine parameters such as the elastic modulus and Poisson ratio as a function of stress. Furthermore, these data can be used to derive an understanding of yield/fracture and the effect of rate on the yield/fracture surface. The work presented is a first step, and is

Jan 1, 1972

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

THE problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce light-weight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough so that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, particularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating." The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. Commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the purpose of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By Cyril Smith

ISOLATED alloys of copper and silicon were prepared and examined by chemical methods more than one hundred years ago, but it was not until the work of Rudolfi1 that the equilibrium relations. were studied. The early history of the alloys was well described by Baraduc-Muller2 PERCENT SILICON-BY WEIGHT FIG. 1.-COPPER-SILICON EQUILIBRIUM DIAGRAM ACCORDING TO RUDOLFI (1907). and need not be further discussed here. The diagram of Rudolfi, based entirely on thermal observations, showed silicon to be soluble in copper up to 4.5 per cent. at 849° C., at which temperature there was a peritectic horizontal resulting from the formation of a 0 phase with about 7.4 per cent. silicon from a and liquid with 7.85 per cent. silicon. The ß phase was believed to form a eutectic with Cu3Si at 820° C. and 9.8 per

Jan 1, 1928

By S. Terry, W. Callender, R. J. Cornelius

When a dry ball-mill grinding circuit was in- stalled at the pellet plant of Hamersley Iron Pty. Ltd., it was something of a pioneering venture, since this was one of the first instances where such a circuit had been applied to iron ore on a major scale. The Hamersley pellet plant is located in Dampier on the coast of Western Australia. The feed for it consists of -8mm fines produced as a screened product at the Mt. Tom Price mine 186 miles inland from Dampier. It was these fines that encouraged the choice of a dry grinding facility for the plant. At the outset, tests had shown that the fines could not be filtered satisfactorily with a wet grinding system. At the pelletizing plant, the fines are stockpiled, reclaimed, dry ground in ball mills, formed into pellets on balling discs, hardened on an indurating line, and stockpiled for shipment overseas. These operations are shown in Fig. 1.

Jan 7, 1969

By A. C. Bulnes

This paper applies the methods of statistical analysis to the interpretation of core analysis data of dolomitic limestone from the San Andres formation at Wasson and the Clearfork formation at Fullerton. Probability relationships are shown to connect the porosity and the permeability and the porosity and the fluid saturation. For example, the porosity-permeability relationship expresses the probability that a sample of porosity,f, will or will not be permeable. The over-all porosity frequency distribution of the reservoir together with the frequency curves of permeability (one for each class interval of porosity) provide a precise basis for computing the weighted average productive porosity of the reservoir for any assigned value of the minimum productive permeability. The probability that the permeability of a core specimen from Fullerton will exceed a given value appears to be dependent on the percentage porosity of the specimen, its void structure type (i.e., porosity in the qualitative sense), and the given value of the permeability. If continuous profiles of void structure type and porosity are available together with the appropriate porosity-probability of permability plots, the nes pay thickness may be estimated. The Invasion Index of a well is defined in terms of the porosity and permeability data. This index is suggested as a basis for comparing wells as regards their suitability as fluid-injection wells. Three problems of importance in the exploitation of limestone reservoirs may be stated as follows: 1. The determination of the productive porosity of the reservoir. The productive porosity is defined as f = fPVP/V [II in which Vp, is the volume of the reservoir that is sufficiently permeable to oil to give up an appreciable fraction of its original oil in place during the economic life of the reservoir; fp, is the arithmetic mean porosity of the permeable volume v*, and V is the total volume of the reservoir. 2. The determination of the number of feet of oil-bearing porous rock that will produce at a commercial rate into the well bore; i.e., the net pay thickness. 3. The choice of fluid-injection wells in a secondary recovery program. The ultimate recovery of the reservoir is proportiona1 to the productive porosity. The productive capacity of the well is proportional to the net pay thickness. The principal purpose of this paper is to show that the methods of statistical analysis when applied to core analysis data of dolomitic limestones offer a useful approach to the solution of these three problems, as well as others of importance in reservoir engineering. The use of these methods was suggested by the work of Jan Law.1

Jan 1, 1946

By A. C. Bulnes

This paper applies the methods of statistical analysis to the interpretation of core analysis data of dolomitic limestone from the San Andres formation at Wasson and the Clearfork formation at Fullerton. Probability relationships are shown to connect the porosity and the permeability and the porosity and the fluid saturation. For example, the porosity-permeability relationship expresses the probability that a sample of porosity,f, will or will not be permeable. The over-all porosity frequency distribution of the reservoir together with the frequency curves of permeability (one for each class interval of porosity) provide a precise basis for computing the weighted average productive porosity of the reservoir for any assigned value of the minimum productive permeability. The probability that the permeability of a core specimen from Fullerton will exceed a given value appears to be dependent on the percentage porosity of the specimen, its void structure type (i.e., porosity in the qualitative sense), and the given value of the permeability. If continuous profiles of void structure type and porosity are available together with the appropriate porosity-probability of permability plots, the nes pay thickness may be estimated. The Invasion Index of a well is defined in terms of the porosity and permeability data. This index is suggested as a basis for comparing wells as regards their suitability as fluid-injection wells. Three problems of importance in the exploitation of limestone reservoirs may be stated as follows: 1. The determination of the productive porosity of the reservoir. The productive porosity is defined as f = fPVP/V [II in which Vp, is the volume of the reservoir that is sufficiently permeable to oil to give up an appreciable fraction of its original oil in place during the economic life of the reservoir; fp, is the arithmetic mean porosity of the permeable volume v*, and V is the total volume of the reservoir. 2. The determination of the number of feet of oil-bearing porous rock that will produce at a commercial rate into the well bore; i.e., the net pay thickness. 3. The choice of fluid-injection wells in a secondary recovery program. The ultimate recovery of the reservoir is proportiona1 to the productive porosity. The productive capacity of the well is proportional to the net pay thickness. The principal purpose of this paper is to show that the methods of statistical analysis when applied to core analysis data of dolomitic limestones offer a useful approach to the solution of these three problems, as well as others of importance in reservoir engineering. The use of these methods was suggested by the work of Jan Law.1

Jan 1, 1946

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

Bellows Connector Fabricated of chemically inert Teflon, the new bellows type connector has many pipe line applications where vibration, expansion and electrolysis exist in the handling of corrosive liquids or gases and solvents. The new connector is electrically non-conductive, flexible even at 94°F and as strong as 480°F as at 70°F, according to the manufacturer. This bellows connector serves as a [ ] vibration dampener as well as an expansion joint and connects misaligned couplings and insulates flanges electrically. End flanges of the joint are French-type envelope gaskets made integral with the joint for easy assembly between companion flanges and a tight, leak-proof seal on installation. Circle No. 1

Jan 1, 1952

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By Andrews Allen

WE all remember when, a few years ago the preparation of coal was nothing but a matter of having somebody at the face or somebody in the railroad car pick out the impurities; also the sizes were generally' made" over a bar screen. Anything that was black was coal; and the only matecia1 picked out was the slate or rock-impurities that could be distinguished by eye or by hefting. This was all right as long. & coal could be sold at. a good price. After all, we are all in business to -make the most money honestly out of a certain acreage of coal and a certain plant. For this purpose what is required is the greatest possible recovery of marketable coal and the highest market price.

Jan 1, 1929