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By P. E. Senseny

INTRODUCTION Massive hydraulic fractures have been used since 1949 in the petroleum industry to enhance production rates and increase recoverable reserves. Currently, a research program, the Multi-Well Experiment, is underway to develop the understanding and technology to a1 low economic production of the large gas reserves of the low permeability, lenticular sandstone formations in the western U.S. (Atkinson, et al, 1981; Northrop and Sattler, 1983). Use of state- of-the-art hydraulic fracturing techniques is a part of this investigation. As a portion of an extensive core program in support of this experiment (Sattler, 1983), fracture toughness has been determined for 56 sandstone, shale, mudstone, or siltstone horizons from three wells in the Piceance Basin. The role of fracture toughness in hydraulic fracturing is not well understood because other factors, such as in situ stress, dominate fracture geometry and containment. Rubin (1983) concluded from analysis of his laboratory hydrofracture experiments that fracture toughness should be included in design and numerical simulation of hydraulic fractures. However, van Eekelen (1982) contends that the stress intensity at the crack front should be so much greater than the fracture toughness of the rock that toughness can have no importance. Generally, fracture toughness and other material properties, such as elastic moduli and permeability, are thought to be of secondary importance in determining fracture geometry and containment. In spite of this, there is a need to acquire a more quantitative understanding of their importance for accurate design and simulation calculations. Analysis of fracture geometry and containment data from hydraulic fracturing experiments carried out in formations where fracture toughness and other rock properties are

Jan 1, 1984

By Wayne Loel

THE application of aerial photographs to all phases of geologic mapping is set forth, indicating the advantages to be gained in different types of country and under varying climatic conditions, Methods of field and office procedure are given from a geological point of view, as well as suggestions regarding the best methods of aerial mapping for different uses and under varying field conditions, including the study of submarine geology. Aerial photographs with accompanying geologic maps are shown to illus-trate the appearance from the air of different geologic features under varying climatic and topographic conditions.

Jan 1, 1938

By J. D. Embury, R. M. Fisher, A. S. Keh

An investigation of the defect structure and properties following large strain deformation has been carried out using transmission electron microscopy and mechanical testing for a range of ferrous materials and for copper. It is shown that, for a variety of ferrous materials, a cellular substructure is developed during the initial stages of working and on further deformation the dimensions of this substructure are reduced. Quantitative measurements of the flow stress and the scale of the substructure indicate that the strength of heavily worked materials is largely determined by the spacing of cell walls. These cell walls act as dislocation barriers in a manner analogous to grain boundaries. FCC materials do not harden as extensively as bcc after cold working and the present observations on copper indicate that the dimensions of the substructure in fcc materials are not markedly reduced on deformation. The differences between the fcc and bcc structures produced by large plastic strains are ascribed to differences in the extent of dynamic recovery. It is tentatively proposed that the greater stability of substructural barriers in bcc structures results from strong interstitial Pinning effects. It is proposed that for large plastic strains the work-hardening process may be considered in terms of the reduction of substructural-barrier spacing during the working process. This pvovides a simplified hut useful analysis of the strain hardening occurring during mechanical processes. THE mechanisms of strain-hardening processes have occupied the attention of numerous investigators over the past three decades and a multitude of theories have emerged in this field. The majority of previous work has been concerned with the development of a description of the plastic behavior of single crystals in terms of dislocation theory.'" In contrast, scant attention has been given to the strengthening mechanisms operative during mechanical working processes such as rolling and drawing. The large plastic strains involved in these processes make it difficult to correlate the observations with any elementary dislocation theory. Further, as Bullen and coworkers3 have opined, for large plastic strains both hardening and recovery occur simultaneously and thus it is extremely difficult to estimate the effect of plastic strain on the ambient internal stress field. It is probable that for large plas- tic strains any theoretical estimate of the internal stress field must be made in terms of complex dislocation groups. Although some valuable theoretical work has been done toward calculating the elastic properties of dislocation groups4 any detailed self-consistent model for large plastic strain is as yet impossible. With these limitations in view it is still of value to examine the mechanical properties of highly strained materials as a function of their substructure. This relationship is explored in the present communication for a variety of materials subjected to rolling, drawing, or swaging. The primary object of this investigation has been to establish the validity and the limitations of the substructural strengthening mechanism proposed by Embury and eisher' for drawn pearlitic wire and by Meieran and Thomas for drawn tungsten wire. No attempt has been made to delineate the basic interaction mechanism which occurs between a slip dislocation and the substructure and the authors believe that a great deal more experimental evidence must be compiled before these fundamental aspects can be explored. Also, no specific attention has been given to the detailed formation of substructure during working. Experimental Details. A variety of materials were used in this investigation, the compositions and heat treatment of which are tabulated in Table I. The commercially pure iron is referred to throughout this report as Ferrovac E. The mechanical working processes were all performed at room temperature. The wire drawing was performed on a manual drawing bench. Reductions of between 10 and 20 pct in area per pass were used in both swaging and drawing. The experimental parameter used to evaluate the mechanical properties of the materials was the 0.2 pct proof stress. This was determined for wire samples using an Instron tensile machine at a crosshead speed of 0.02 in. per min. The techniques for preparation of samples for transmission electron microscopy have been described previo~sl~.~ Specimens from wire samples were prepared from longitudinal sections and in some cases from transverse sections. To evaluate the substructural characteristics of rolled materials, thin foil samples were prepared of both the face and edge sections. Results. One of the more familiar ways of expressing work hardening in mechanical working is by the flow stress as a function of reduction in cross-sectional area. Fig. 1 shows such a plot for Ferrovac E eutectoid carbon steel and for copper. The curve for Ferrovac E is characterized by an initial stage of rapid work hardening and a final stage of rapid work hardening separated by an intermediate stage with a low rate of work hardening. This behavior is typical of many ferrous materials and the drawn pearlite wire previously investigated by Embury and Fisher is a more pronounced example. Copper shows an initial

Jan 1, 1967

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By C. A. Stetefeldt

In May and June, 1885, I was engaged in examining the goldores of Las Minas, in the State of Vera Cruz, Mexico, with a view of finding a cheap and efficient method for extracting the gold. The following minerals could be plainly seen in the ore : magnetite, pyrites of iron, pyrites of' copper, quartz, and garnet. Neither galena nor zinc-hlende mere visible, but the ore contained a trace of lead, and in some samples of ore from the Muertos mine, 1.19 per cent. of zinc mas found. Antimony and arsenic were not present. Native gold could scarcely be seen in specimens of' the ore, and it only appeared—mainly in extremely fine particles—after pulverizing and washing. Magnetite was in every instance the most prominent mineral, its quantity varying between 43 and 67 per cent. Determinations of copper and sulphur showed that from 3.5 to 7 per cent. pyrites of copper, and from 3 to 22 per cent. pyrites of iron were present. The gold-value of the ore varied between 0.3 oz. and 0.8 oz. per ton. I do not speak of specimens, but of average samples of large quantities of ore put through the battery. In ore that had been crushed through a No. 40 screen, the gold appeared, in part, as free gold, the rest being thoroughly mixed with the magnetite and pyrites, both minerals containing about the same percentage of gold. If this free gold was brought in contact with pure quicksilver it (lid not amalgamate readily, even if the quicksilver was charged with sodium amalgam.

Jan 1, 1886

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By C. E. Lesher

Low-temPeRatUre carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus ?-in. or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal. of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic consumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold. Acknowledgments During the 10 years in which the work that is summarized in this paper has been under way, many have contributed time and effort, faithful service and fruitful thinking. Whatever success has attended

Jan 1, 1940

By C. E. Lesher

Low-temPeRatUre carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus ?-in. or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal. of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic consumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold. Acknowledgments During the 10 years in which the work that is summarized in this paper has been under way, many have contributed time and effort, faithful service and fruitful thinking. Whatever success has attended

Jan 1, 1940

By R. E. Schilson, F. H. Poettmann

The direct determination of the stabilized performance behavior of low capacity, slowly stabilizing gas wells is extremely time-consuming and wasteful of gas. From both field experience and theoretical considerations, a test procedure has been evolved by which the stabilized hack pressure behavior of such gas wells can he predicted without having to revert to long time flow tests. The method consists of using the isochrona1 test procedure to establish the slope of the back pressure curve, "n", and the short time variation of the performance coeficient, "C", with time. From this short time transient flow data and theoretical considerations, the value of C at large times can he established. By assuming the radius of drainage of a well to be half the distance between wells, one can calculate the stabilization time for various well spacing patterns. Once the stabilization time for a given .spacing has been determined, the value of C can be calculated and the stabilized back-pressure curve can he. establbrhed. The calculated perfortnance coefficient as a function of tinze was cotnpared to the experintentally measured values for a number of gas wel1.e. The deviation of the calc~*lated from the cxperimental res1tlt.s vary depending on the set of short time experimental points used to evabrate the parcrttzeters of the equation. The longer the tirne far the flow test data user1 in the calculations, the better was the agreement with the experimental results. The time necessary to obtain this data from well tests varies consitlerably, depending on the physical natrcre oj the rt3scrvoir under consideratiot~. INTRODUCTION For many years, the U. S. Bureau of Mines Monograph 7' has served as a guide for testing and evaluating the performance of gas wells by means of the back-pressure method. The back-pressure performance of a gas well is expressed by the following equation: Q~ CW-W.........(I) where the characteristics of the back-pressure equation are determined by C, the performance coefficient, and n, the exponent which corresponds to the slope of the straight line when Q and {P* - PN2) are plotted on logarithmic paper. Q is gas flow rate at standard conditions, and P, and P, are equalized and flowing bottom-hole pressures, respectively. Prior to the development of the back-pressure tcst, the "open flow" capacity method of testing a well was common. By this method, the wells were flowed wide open to the air and the flow rate measured. Such procedure was wasteful of gas and did not provide information on the deliverability of the gas to the pipe line. Monograph 7 Procedure The back-pressure method of testing wells was developed to overcome these shortcomings. Although much has been learned regarding the laws of the flow of gas through porous formations, the original development of the back-pressure relationship was based entirely on empirical methods. The back-pressure behavior provides the engineer with information essential in predicting the future development of a field. It permits him to calculate the deliverability of gas into a pipe line at predetermined line pressures, to design and analyze gas gathering lines, to determine the spacing and number of wells to he drilled during the development of a field to meet gas purchasers' requirements, and to solve many other technical and economic problems. As described in Monograph 7, the flow-after-flow method of back-pressure testing, when applied to fast stabilizing and usually high capacity wells, correctly characterized the behavior of the well. However, as the value of the gas at the wellhead increased, small capacity gas wells having slow rates of stabilization became economically operable. The flow-after-flow method of testing could not be used to describe the behavior of these slowly stabilizing wells. The procedure of Rawlins and Shellhardtl for establishing the back-pressure behavior of a gas well was based on the rcquirement that the data be obtained under stabilized flow conditions; that is, that C is constant and does not vary with time. C depends on the physical properties of the reservoir, the location, extent and geometry of the drainage radius, and the properties of the flowing fluid. In a highly permeable formation, only a very short period of time is required for the well to reach a stabilized condition, and, consequently, the requirements for the test procedure described in Monograph 7 are met. For a given well, n is also constant

By Leroy U. Gardner

EVERY reader of this paper is well aware of the fact that the prolonged inhalation of large amounts of free silica dust results in fibrosis of the lungs, and that other inorganic dusts, except those of asbestos and the mineral poisons, are thought to be relatively harmless. But probably few have had opportunity to visualize the effects of silica, asbestos and other minerals upon living tissues. The ideal demonstration would be based upon sections of lungs from human beings that had inhaled com- parable concentrations of different dusts for a unit period of time. Such material is generally difficult to obtain and in some instances is of questionable value because the subject has been exposed to more than one kind of dust. A demonstration could be prepared from the lungs of animals. However, so many months or even years are required to complete the exposure to each kind of dust that enough material has not been accumulated. For a general survey of the action of different types of dust, I am therefore compelled to use the tissues of animals that have been injected with suspensions of dust particles. The injection method offers certain advantages. The quantity, the particle size and the state of dispersion can be controlled with sufficient accuracy so that the tissue responses to different minerals can be accurately compared. The method insures contact between the tissues and the mineral particles; protective mechanisms, which may prevent the inhalation of certain types of foreign body, never come into play. If the pathway of injection be one that minimizes nonspecific injury, the tissue responses may simulate those produced by inhalation but they develop somewhat more rapidly. It should always be remembered that injection methods merely demonstrate the capacity of various kinds of minerals to provoke reaction in the tissues; whether the same substances are inhaled from atmospheric suspension and accumulate in the lungs in dangerous quantities can be demonstrated only by inhalation. The reactions that I shall discuss first took place not in the lungs but in the liver. For the purpose in hand this is quite immaterial for we are merely seeking to discover whether these minerals are capable of produc-

Jan 1, 1938

By C. Chiou, D. P. Seraphim

The effect of clustering on the superconducting properties of Al-Zn alloys has been studied by the ballistic induction techniques. The superconducting critical temperature, T,, changes when zinc-rich clusters are formed. The change in T, depends on the concentration and may be positive or negative, but always correlates with an effective decrease in the solute concentration of the alloy. Reversion after clustering effectively returns a 5 at. pct Zn alloy to the quenched state. These methods might be use&lly extended to the Al-Mg system, where X-ray data are difficult to obtain. In very dilute Al-Zn alloys, as in other tin,' indium, aluminum,2 or tantalums base solid solutions, there is a decrease in the superconducting critical temperature, Tc, roughly proportional to the temperature independent resistivity, i.e., -0.2°K per pS2cm. With increasing solute concentration, the T, generally reaches a minimum and then increases4 to a value well above that for the pure solvent. The change of T, with solute concentration follows an empirical formulation involving two constants which correlate with the scattering cross section of the impurities. As will be shown below, the Al-Zn alloys more concentrated than 1or2at. pct do not follow the empiricism, probably because they are unstable even when rapidly quenched.5 However, it seems possible to study at least the later stages of solute clustering by precise measurements of the 1', following various thermal treatments. A few experiments on quenched alloys, aged alloys, and tests on reversion are reported here. The heat treatments selected for obtaining the quenched and aged states were mainly deduced from the work of Dash and Fine.6 For the quenched state, specimens were homogenized at 480°C, quenched to -160°C, and immediately transferred and mounted in liquid nitrogen. Measurements on the superconducting properties and residual resistivities were then made at helium temperatures, after which the specimens were aged at room temperature for 3 to 5 hr, i.e., much longer than the time required for clustering to be essentially completed. The superconducting properties and residual resistivities were once again examined. To reach the reverted state of the A1-5at. pct Zn alloy, the aged specimen was heated for 5 min at 200°C and then tested as above.

Jan 1, 1963

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger's grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger' s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By Edward H. Robie

SUBJECT to formal Board approval in September, AIME dues will continue indefinitely at the present scale of $20 for Members and Associate Members; and $12 for Junior Members for the first six years of such membership, thereafter $17. That is the wish of the Board of Directors and the will of the membership, as expressed in the recent referendum. Though the official returns, as reported by the tellers, are not available as this is written, the data are sufficiently complete to give the results to the nearest percent. The total vote was approximately 93 pct for continuance of the present scale. Metals Branch members voted about 94 pet for continuance; Mining Branch members slightly less than that; and Petroleum Branch members about 91 pct. As in the referendum of 1949, there was no particular difference of opinion on the question of dues as between the three Branches. The percentage of ballots returned was about 61 pct, only slightly more than in the 1949 referendum. But the affirmative vote was much greater, 93 pct against 78 pet in the earlier referendum. Looked at another way, a majority of those to whom ballots were sent, 56 pct, voted to continue the present scale of dues, whereas only 46 1/2 pct of those canvassed voted to raise the dues in the previous referendum. But approximately 600 , members expressed their opinion that the dues should go back to $15 for Members and Associate Members and to $10 and $15 for Junior Members. This is a substantial group of members who either do not think they are getting their money's worth from AIME membership, or believe that a more businesslike conduct of Institute affairs should provide current services at less cost, or believe that more service is being provided for their dues than they need. As to the first point, it is probable that some members are not getting their money's worth. They perhaps have only a fringe interest in. AIME activities, or they do not or cannot participate in such activities at the Local Section, divisional, or national level, so that all they get out of the Institute is the monthly journal, which they do not have time to read. If they did read it intelligently, and acted upon the professional information thus gained, it is difficult to understand how one or more ideas cannot be gained that would be worth $20 to them professionally. But the 600 members who want lower dues offer a challenge to the Directors and to the staff to do a better job; to make Institute membership so rewarding that every. member will be thoroughly satisfied. Twenty 1935 to 1939 dollars are worth only $11.60 now, according to the latest government data, but that makes it all the more necessary for us all to appraise the value of what we buy. To the 93 pct of Institute members who expressed a vote of confidence, so to speak, the staff, and we feel sure the Directors as well, are most appreciative and thankful.

Jan 1, 1952

By O. B. Bucklen, P. G. Meikle

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also held true for loading and storage facilities. Where once a million ton per year mine was rare, three to five million ton per year mines are not uncommon today in the bituminous industry. This greatly increased production, made possible through mechanization, required greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend toward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw coal storage and blending facilities. The development of the unit train with its attendant economics, more than any other factor, has contributed to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has contributed to a need for faster and larger loading facilities. In this climate of rapidly changing technology, any written account is faced with the possibility of obsolescence before its appearance. Thus, this chapter seeks to define the common and current practice in coal loading and storage facilities with the full knowledge that this practice is an ever-moving target. FUNDAMENTALS OF COAL STORAGE Storage of coal is becoming an increasingly important part of coal handling systems at mines, particularly since the advent of the unit train concept in transportation. In order to take advantage of reduced transportation rates on trainload shipments of coal offered by unit train movement, operators have found that storage is an economic necessity. In unit train practice large predetermined quantities must be loaded in relatively short periods of time as opposed to conventional practice where coal is loaded at a speed dependent on the production capacity of the mine and/or the cleaning capacity of the preparation plant. Two surveys of storage practices at mines reveal several objectives for storage.1, 2 Raw and/or clean coal storage is generally practiced in order to accomplish one, or a combination, of the following objectives: 1. To improve plant efficiency by distributing plant feed over the entire operating time, or to allow a preparation rate different from the production rate. 2. To limit interruptions of supply, ie, allow mine and plant to function independently with delays in one not affecting the operation of the other.

Jan 1, 1968

By Herbert Clark Hoover, Lou Henry Hoover

DIFFERENT methods of parting gold from silver, and, on the other hand, silver from gold, were discussed in the last book; also the separation of copper from the latter and further, of lead from gold as well as from silver ; and, lastly, the methods for refining the two precious metals. Now I will speak of the methods by which silver must be separated from copper, and likewise from iron.1 The officina, or the building necessary for the purposes and use of those who separate silver from copper, is constructed in this manner. First, four long walls are built, of which the first, which is parallel with the bank of a stream, and the second, are both two hundred and sixty-four feet long. The second, however, stops at one hundred and fifty-one feet, and after, as it were, a break for a length of twenty-four feet, it continues again until it is of a length equal to the first wall. The third wall is one hundred and twenty feet long, starting at a point opposite the sixty-seventh foot of the other walls, and reaching to their one hundred and eighty-sixth foot.

Jan 1, 1950

Report of the Secretary TO THE BOARD OF DIRECTORS AND THE MEMBERS OF THE AMERICAN INSTI¬TUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN As will be shown by the special reports of the Finance, Membership, Library, Papers and Publications, Increase of Membership, and other standing Committees, together with that of the Treasurer, the year 1927 was one in which the Institute made very satisfactory progress in a number of directions. In total numbers the membership is no larger but in revenue from dues there has been a marked increase. This has been due to the promotion to full membership of Junior Associates of earlier years, to the larger proportion that come in originally as members rather than juniors, and to the keener interest in the work of the Institute reflected in prompter payment of dues. The latter is important, since experience shows that of those who fall behind a large number must ultimately be dropped for non-payment. Conditions in the mining in¬dustries have been healthy though not booming. It has been much easier for members to find employment and meet their financial obligations but there has not been that flow of young men into mining, and hence in part into the Institute, that characterized certain earlier years. Rather the tendency toward centralization and larger industrial units has re¬stricted the number, though not the scope, of opportunities for technical men in the mineral industries. The Institute is constantly receiving resignations from members crowded out of mining into other lines of activity. On the other hand, those who remain in mining and metal¬lurgy have a greatly increased necessity for information and contacts with technology. A few years ago many superintendents and most foremen were non-technical men. Today the reverse rule obtains and shift bosses and men who occupy even lower positions in industrial units are called upon to know and to apply such an amount of technical knowl¬edge that graduate engineers are the rule rather than the exception. The curious situation has obtained that with a much smaller enrollment of students in the schools of mining and metallurgy there has been at times an actual shortage of young engineers for beginners' jobs. The young men retort that the conditions of employment and pay offered in mining are not equal to those in other lines and, while it is undoubtedly true that the young engineer beginning in mining is able to start under conditions markedly better as to pay, living, and responsibility than did the men who are now leaders, they are required to know much more and have usually spent more in time and money to qualify for their jobs. The whole matter is one which warrants much more attention than has been given to it. For the Institute it is important since the young men

Jan 1, 1923