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By A. W. H. Morris, E. A. Steigerwald

The jatzgue beizazriov oj Mietal matrix co))zpos~tes in tension -lensiom loading has been imestigated as a junction of Dolume fraclion veinfovcelnent using the model systems of a silver matrix reinforced with contlnuous or dzscontztinuous aligned tungsten jilamenls and continuous aligned steel filamenls. Appreciable impvocetnents in fatigue strength were obseved in all syslems inzvesLigated, the degree of sl renglhenng-increasing with increasing volume fraclion of reinforcement. The mode of fatigue failure was found to be a function of colutrre jp-actiotz and was also noted to be controlled by the relative fatigue and strength characlerislics of the matrix and reinforcemenl. THE advantages to be gained by suitably incorporating high-strength filaments or whiskers into metallic matrices are well-recognized.' To date emphasis has been placed on the experimental determination of tensile strengths and elastic moduli of metal matrix composites measured parallel to unidirectionally aligned filaments. Several attempts have been made to relate experimentally measured tensile properties to theoretical values calculated from the properties of the components on the basis of the relatively simple "rule of mixtures" analysis. However, relatively few data have been reported in the literature on the fatigue behavior and mechanism of fatigue failure of metal matrix composites. In a study of fatigue crack propagation in aluminum plus steel wires and aluminum plus tungsten wires, Forsyth et a1.2 found that the incorporation of small numbers of filaments suitably dispersed were capable of substantially reducing the rate of fatigue crack propagation. For this purpose, the strength of the filaments appeared to be more important than the aspect ratio and the authors reported that parallel filaments were not the most favorable orientation for increased strength. In a basic study of the fiber reinforcement of metals, Williams and 0'brien3 report preliminary results which indicate a considerable improvement in fatigue strength in reversed bending fatigue of a steel wire-reinforced aluminum alloy composite. In a study of the influence of interfacial bonding on fatigue behavior, Baker4 has also reported improved fatigue properties in stainless steel-reinforced aluminum composites. In contrast, Ham and place5 report that, although tensile properties are improved greatly by filament reinforcement, the reinforcement of copper with continuous, brittle tungsten wires up to 23 vol pct was comparatively ineffective against fatigue. The authors attribute the poor fatigue properties of the composite to fatigue hardening of the matrix at the tips of cracks which can build up stress concentrations sufficiently large to fracture proximate filaments. Baker and cratchley6 failed to find marked improvements in the reversed-bending fatigue properties of silica-reinforced aluminum. The study was complicated by the complex behavior in a composite during the compres-sive half-cycles imposed in this type of loading. This was manifested in the failure of the composites by de-lamination, a contributing factor being the presence of aluminum oxide at the matrix-filament interface. Prior to the general acceptance of filament-rein-

Jan 1, 1968

By R. J. Hafsten, E. S. Davenport, R. A. Grange

THE influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,1 and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely retarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths, Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745°F. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245°F. (675°C.), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarse-grained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite-that is, at temperature levels above about 1000°F. (540°C.)-but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to be presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000°F. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. MATERIAL AND EXPERIMENTAL PROCEDURE The material investigated was a commercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent M0. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By Yves Dardel

THE literature concerning the remelting of aluminum and its alloys is very rich. Unfortunately the greater part of the papers about this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification1,2 are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges and the atmosphere of the furnaces bring into the bath during the successive remeltings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, .. , if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H2, 02, H2O, C02, CO, CH4, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of Sieverts3 as a function of its partial pressure PH2 in the atmosphere [m = K _%/PH, [I]] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Röntgen and Braun4, Röntgen and Möller5, Bircumshaw6 and Winterhager7 have rendered it possible to determine the value of K, when the temperature is inferior to 1.000°K. One obtains: [log K = - 4,702.5 + 0.238 [2]] Besides its usual signification, the term PH2 represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is, when no gas exchange occurs between the two phases, the pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary occurs, the quantity of H2 should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature lowers, the internal pressure of H2 increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a maximum depending on the hydrostatic pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However, even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1947

By T. L. Joseph, G. Bitsianes

THE layered structure of partially reduced iron ore was described in a previous paper.' Reduction by hydrogen was found to take place at well-defined interfaces between layers of the solid phases. In the present investigation, a detailed study was made of the wiistite phase that had formed during the partial reduction of a cylindrical compact of chemically pure hematite. An unusually wide band of wiistite permitted a rather detailed study of this phase. The specimen was made from Baker's C.P. hematite in the form of a cylinder 1.5 cm in diameter and 1.8 cm long. A dense ore structure with about 6 pct porosity was attained by heating the specimen in air at 1100°C for 3 hr. To confine reduction to the top surface, a ceramic coating was applied to the bottom and sides of the cylindrical compact. The specimen was then partially reduced in hydrogen at 850°C and subjected to a coordinated sequence of macro-, micro-, and X-ray examinations. A section of the partially reduced cylinder is shown in the macrograph, Fig. 1. Four layers consisting of metallic iron, wustite, magnetite, and unreduced hematite are clearly shown. The effort to force reduction to proceed downward in topochemi-cal fashion was only partly successful, as some reduction occurred along one side and bottom of the cylinder. A rather wide layer of dark wustite phase had formed, however, and permitted sampling for X-ray studies as indicated. To supplement previous work and to study the wustite layer in more detail, ten separate layers were removed for X-ray examination. Broad and diffuse patterns were obtained with the as-filed powders, especially with those of iron and wiistite, and the condition indicated a cold-working and variable composition effect within the respective layers. This condition was corrected by annealing the entire series of powders at an appropriate temperature. For the annealing treatment, the ten powder samples were wrapped in silver foil, sealed under vacuum in small quartz tubes, and heated at 750°C for 16 hr. The specimens were then drastically quenched in cold water to preserve the annealed condition. These annealed specimens were X-rayed in turn and the compiled patterns are shown in Fig. 2. The standard patterns for iron and its oxides have been interjected at appropriate positions for purposes of comparison and phase identification. All of the patterns obtained were clearcut and concise so that positive identifications could be made for all of the phases. The outermost layers A, B, and C were composed almost entirely of iron with a small amount of wiistite being detectable at the X-ray limit of phase detection. Layer D from the iron-wustite interface showed both of these phases. The next four layers E, F, G, and H were all in the dark phase band which had been tentatively identified as wustite by the macroexamination, Fig. 1. The diffraction data with their single-phase patterns of wiistite for these layers checked the visual evidence. Continuing the X-ray analyses after layer H, the macrograph (Fig. 1) shows that layer I came largely from the magnetite zone but included some fringes of the wiistite-magnetite interface. The diffraction pattern for the sample confirmed this observation. Layer J came from the unreduced core of the specimen and its diffraction pattern indicated a preponderance of hematite phase. The reduction behavior of synthetic compacts has thus been found to be similar to natural dense iron ore. The previous results were supplemented with measurements of the diffraction films and calculations of the respective unit parameters. These X-ray data are summarized in Table I and offer some interesting correlations as to the compositions of the various phases undergoing reduction. The iron layers that were analyzed gave lattice parameters close to that of pure iron at 2.8664A. Evidently this iron was present in layers A through D as a pure phase with little or no oxygen dissolved in its lattice. With the wiistite layers an entirely different situation prevailed in that there was a definite and

Jan 1, 1955

By R. P. Carreker, R. W. Guard

True stress-true strain data are given for nominally pure molybdenum (99.95 pct) over the temperature range -196° to 1540°C (0.027 to 0.63 T/T). Strain rate sensitivity was determined by rate change tests and stress relaxation tests. Inhomogeneous yielding and strain aging effects were observed. The yield stress and tensile strength depend markedly on temperature below 400°C and are insensitive to temperature in the range 400' to 800°C. The ductile to brittle transition range is +25O to -25OC. Strain rate sensitivity and stress relaxation effects are very large near room temperature. THIS report presents data which were obtained as a part of a continuing program designed to document the deformation behavior of nominally pure metals over a wide temperature range.'" This research program is rooted in the conviction that sufficient tensile and creep data of appropriate quality and detail does not exist to provide precise phe-nomenological descriptions of the deformation behavior of pure metals as a function of temperature, strain rate, and grain size. Such knowledge is needed to provide a firm base for alloy design and an experimental framework to which theories of deformation must conform. These data also complement a parallel exploratory program investigating the properties of refractory metals, including molybdenum, and their alloys. Several important reviews and research reports dealing with the tensile properties of molybdenum as a function of temperature have appeared."-lo To a great extent the work to be reported in the present paper parallels that of Bechtold and of Pugh. The authors' results are in general agreement with those of Bechtold and Pugh. The principle differences be- tween the present experiments and those published previously are as follows: 1—Wire specimens prepared from arc cast molybdenum were used in the present experiments, bar specimens were used by others. Pugh used arc cast material while Bechtold's most extensive results" were obtained on powder metallurgy specimens. 2—Several different grain sizes were tested in the present experiments. 3—The testing range was extended to cover from -196°C to 1570°C (0.027 to 0.63 T/Tm). 4—The combination of wire specimens, high speed autographic recording, and a stiff testing machine permitted more detailed study of initial yielding. The principle contribution of the present paper is the demonstration of the relatively consistent mechanical properties of nominally pure arc cast molybdenum specimens of differing metallurgical history. Bechtold and Scotts have shown that arc cast and powder metallurgy molybdenum samples have comparable tensile properties in the range —75" to 200°C when processed to have the same re-crystallized grain size. Material The molybdenum used in this investigation was supplied by the Climax Molybdenum CO. Its metallurgical history is outlined in Table I; the final products were 0,030 in, diam wire specimens annealed at 1100' and 1375°C and 0.060 in. diam wire

Jan 1, 1957

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963

By R. W. Smashey, B. J. Piearcey

The structure, composition, and morphology of the carbide phases present in the nickel-base superalloy, Mar-M200, hare been determined and three carbide phases observed. The MC carbide is a solidification product, and the M23 Co and M6C carbides are both prod~icts of solid-state precipitation. The identity of each phase usas determined by both X-ray and electron-diffraction techn~ques. Compositions of all three carbides were studied using the electron beam micro-probe analyzer and by unalyszs of electrolytically extracted residues. Optical and electron microscopy were employed in order that the time/temperature -dependent behavior of the carbides might be observed. Supplementary studies were completed on thin foils and oriented single crystals to determine the mor-phology and orientation relationship of each phase with that of the matrix. MAR-M~OO* is a high-temperature, creep-resistant superalloy designed for use in the as-cast condition. The "as-cast" microstructure consists of a solid-solution matrix, referred to as gamma (y), which contains a general, coherent precipitate of the inter-metallic Ni3(A1,Ti) referred to as gamma prime (?). As a result of dendritic segregation during solidification, a degenerate, spherulitic ? -?' eutectic constituent is present at the grain boundaries and the in-terdendritic regions, which is nucleated by the y on the dendrite tips. A primary carbide phase, a solidification product, is also present at the grain boundaries and in the interdendritic areas, and an additional carbide appears at the grain boundaries as a fine discontinuous precipitate. The alloy is particularly susceptible to heat treatment. For example, the mechanical properties of the columnar grained mater- ial are substantially improved by solution heat treatment, followed by an intermediate temperature age. Metallographic examination of heat-treated material reveals, however, that exposure to elevated temperatures has a marked effect on the microstructure of the alloy; in particular, it is observed that precipitation of considerable amounts of various carbide phases occur. The following investigation was carried out to determine the morphology, composition, and behavior of the carbides in Mar-Ma00 as an aid to the determination of their effect on the mechanical properties and stability of the alloy. THE PRIMARY MC CARBIDE The MC carbide phase appears in the interdendritic interstices and the grain boundaries. In directionally solidified Mar-M200 the carbide appears as very small particles in the chilled region, Fig. l(a), whereas in material less affected by the chill, it becomes larger and develops a dendritic morphology, Fig. 1(b). Step polishing of metallographic specimens from this region shows that in directionally solidified material the individual carbide dendrites are connected in a dendritic network within the metallic interdendritic interstices, whereas in material from the chilled region and in conventional Mar-M200 they are discontinuous, isolated dendrites. No orientation relationship exists between the primary carbide and the matrix.

Jan 1, 1968

By W. D. Steele, S. D. Brady

The Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains minable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon-galia Co. thence south and southwest across the state to Wayne Co. near Hunt-ington. The Pittsburgh coal is also minable in the Upper Potomac region but is now practically exhausted there. The total minable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13¼ billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio River as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern West Virginia District comprising Wetzel, Mon-ongalia, Marion, Preston, Harrison, Dodd-ridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 1880 (when the Monongahela River Railroad, now B. & 0. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgan-town and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Mononga-hela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of minable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. Economic Importance The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1949

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

INTRODUCTION The preceding chapters have brought us to a point in the mineral appraisal process where the composited sample values can now be used to estimate the grade and tonnage of the total mineral deposit. There are many techniques whereby drill hole composites and/or other sample data are used to assign grade and estimates to the surrounding rock. Matheron and his students have properly called such techniques extension functions. Before embarking upon a detailed discussion of extension functions, it is necessary that we take time to consider the concept of geostatistics as advocated by George Matheron who developed the "Theory of Regionalized Variables," which he published in 1962 (Matheron, 1971). The concept of regionalized variables has important application in the techniques of mineral appraisal. The position or location of a mineral sample within a deposit can be almost as important as its value. Geostatistics, when defined as "the application of the theory of regionalized variables* to the study of mineralized volumes of rock," takes into consideration the position as well as the magnitude of the value of the sample. The principles of geostatistics, as outlined by Matheron, represent a major step forward in the mineral evaluation process, because they provide a sound theoretical and practical basis for quantifying the geological concepts of (1) area of influence of a sample, (2) the continuity or lack of continuity of mineralization within the ore body, and (3) the lateral changes in mineralization according to the trend direction of an ore body and its orthogonal components; or in other words, a measure of the anisotropy of the deposit. Royle (1971) has defined the objects of geostatistic as being: "1. To estimate the most likely value of blocks of ore, or the values of the whole deposit; and 2. to estimate the errors of such estimates. This latter is important as, in addition to providing a check on unwarranted optimism, it shows where more valuation work may be needed." Because of the great importance of these concepts in mineral evaluation, an introduction into the theory of regionalized variables, and the study of a practical approach to its application is outlined here. REGIONALIZED VARIABLES VS. RANDOM VARIABLES Classical statistics, as discussed in earlier chapters, grew out of the study and application of probability theory. Probability is concerned with the outcome of random events and therefore classical statistics is built upon the theory of random variables, i.e., the probability of independent events. The validity of most statistical inferences depends upon sample randomness being assured for unbiased results. Where independent events cannot be assumed the results of statistical inference becomes suspect. On the other hand, geostatistics is concerned with variables that have position in space as well as magnitude, hence the term regionalized variables. Mineral deposits are not the only field to which the theory of regionalized variables is applicable. Many natural phenomena that demonstrate a relationship between change in magnitude and position in space are amenable to application of geostatistical techniques. Mineral deposits vary greatly in their geosta-

Jan 1, 1980

By W. D. Steele, S. D. Brady

THE Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains mineable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon¬galia Co. thence south and southwest across the state to Wayne Co. near Huntington. The Pittsburgh coal is also mineable in the Upper Potomac region but is now practically exhausted there. The total mineable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13% billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio river as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern. West Virginia District comprising Wetzel, Monongalia, Marion, Preston, Harrison, Doddridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 188o (when the Monongahela River Railroad, now B. & O. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgantown and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Monongahela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of mineable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. ECONOMIC IMPORTANCE The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1948

By John W. Vanderwilt

The unpredictable behavior of ground movement and subsidence has complicated the problems that attend the extraction of large quantities of ore. Special studies, particularly relating to coal mining, have yielded such a voluminous literature and so many involved controversial theories that a partial review would be difficult. Limited space makes any kind of a review impractical. The features to be considered cover only a relatively small part of the broad problems of ground movement and subsidence, but it is believed that this small part is critical. The practical aspects are important, since they bear directly on safety of mine workings, on recovery of ore and on dilution of ore in block caving and related systems for extracting large quantities of rock. The ground movement to be described occurs outside the vertical boundaries of a caved block in the area that is commonly referred to as being in the "zone of draw." "Draw" is a term that originated in the subsidence problems related to coal mining, and it is defined by a line drawn from the margin of the area caved underground to the most distant fracture at surface on the same side of the caved area as shown in Fig. I.' A line thus drawn is called the cave line, and its angle with respect to the horizontal is the cave angle or angle of draw. It is understood that the line is taken normal to the limit of mining, and in a vertical plane. The prevailing theories as to draw and angle of draw assume that appreciable movement occurred along the cave line, which has been described as a fracture resulting from the shearing action brought about by the weight of the overlying load. Fig. 3 shows diagrammatically the mechanics of ground movement adjacent to an area of subsidence according to the prevailing theory of draw (A, from Royce2) and, for comparison, ground movement observed in the Climax mine (B). The text in Peele's Handbook2 referring to Fig. 2 does not state the meaning of the "original position of top of workable ore" in the rectangular space above "ore in place," and the arrows are not explained. However, this presentation is most concerned with the zones outside the rectangle. According to the prevailing theory, as shown at the extreme left under A, Fig. 2, the vertical tension cracks at surface change at a shallow depth to shear fractures forming the cave line, and it is assumed that appreciable movement takes place along the cave line toward and into the subsiding caved block. The mechanics of ground movement observed in the Climax mine, as shown under B, Fig. 2, does not accord with the prevailing theory, particularly as regards the cave angle and draw. The vertical tension cracks seen at surface die out at depths of 150 to 225 ft. and shear fractures do not develop. Movement is confined at surface to a mantle of rock 50 to roo ft.

Jan 1, 1949

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By A. D. Dorenfeld

Factorial design is a mathematical method of drawing valid conclusions from a series of tests made in a predetermined pattern. It is applied to flotation ore testing using, in this case, five variables, each varied twice, requiring a total of 32 tests. Representative conclusions are checked by repeat testing. THE factorial design method of testing is particu-J- larly applicable to mill-scale plant tests because 1—the conclusions take into consideration all variabilities of the plant, 2—there are no subjective guesses as to the conclusions, 3—the number of tests necessary to check large numbers of variables are at a minimum, and 4—interactions between variables can be discerned. It is equally applicable to laboratory testing because once the variables to be investigated have been decided upon, as well as the number of levels for each variable, a well-trained assistant can run the tests, since the test work follows a predetermined mathematical pattern, leaving the conclusions to be found by the person in charge. The conclusion takes into consideration all errors of the tests. To illustrate the use of factorial design, a sample of copper porphyry ore was tested, the copper content of the batches not being uniform. Five variables were investigated, each at two levels, requiring only 32 tests. After suitable arithmetical analysis, conclusions for copper recovery and concentrate grade are arrived at. Four cases of these conclusions are checked by repeat testing. Testing Methods Reproducibility of flotation tests varies widely, depending on the experimenter, the process, the equipment, and probably a host of unknown and perhaps interacting variables. If the reproducibility of tests is good, let us say to 0.2 pct recovery of a certain metal, and the minimum difference between tests upon the variation of the interested variables is, say 1 pct, then simple averaging and inspection is ample in interpreting results. However, often such a happy situation is not the case. This is particularly true in mill-scale operations where the ores are variable, and a host of minor operating fluctuations common to most milling, and familiar to all mill operators, is the normal state of affairs. Yet, mill scale tests are run, the results averaged, and conclusions drawn therefrom. The trustworthiness of such results should be measured by comparison to the experimental error—the measure of the degree of reproducibility of the results. This comparison is a test of significance. Thus, if daily results of recoveries average 80.0 pct, and a spread of 78.0 pct to 82.0 pct, is recorded, then, clearly, on changing mill operations, an 81 pct recovery cannot be construed as significant by using averages, since it is well within the previous test limits. By using rigorous statistical tests of significance, conclusions arrived at by inspection or simple averaging may be shown to be based on inadequate evidence or even wrong. In any event, a plant super-

Jan 1, 1952

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By Ferit Gurses

EXTENSIVE coal and lignite deposits exist in Turkey. Bituminous coal is the nation's principal mineral resource; important not only as fuel for the industrial development of the country, but also as a means of obtaining foreign exchange. Of the electrical power generated during 1939, 82.8 per cent was derived from coal.1 It is anticipated that the lignite deposits will be one of the major sources of power for the electrification of the country. BITUMINOUS COAL The locations of the four principal bituminous-coal2 basins are indicated on Fig. 1. The Eregli-Zonguldak basin lies on the Black Sea northwest of Ankara; the Canakkale basin lies near the junction of the Dardannelles; the Trakya basin is in European Turkey northwest of the Bosphorus and the Erzurum basin lies far to the east. The Eregli-Zonguldak basin is the most important of the four. This coal basin was discovered in 1829 but did not arouse interest until 1848; up to 1865, its annual production had not exceeded 50,000 metric tons. In 1865, during the Sultanate, working of coal mines was started by the Navy department, and the annual production was 61,145 metric tons. In 1908, the Minister of Commerce and Agriculture was authorized to develop the whole coal basin. Production reached 264,397 metric tons in 1910, and during 1915-1922, preceding the revolution, the total production of the basin was 2,676,043, or an average of 334,000 metric tons annually. The period of national revolution that followed was marked by a steady increase in coal production in Turkey, although world production decreased, because of the crisis of 1929-1932, about 52 per cent. AREA AND GEOLOGY OF THE COAL BASIN The geology of the Eregli-Zonguldak area is not yet completely known. The basin begins at Gungazi, to the west of Eregli, and extends to Sogutozu, a distance of about 106 miles. The coal beds, however, appear only in places and the overlying Cretaceous strata hide them elsewhere. This area includes the most important centers, such as Kandilli, Alacaagzi, Teflenli, Kozlu, Gelik (see Fig. 2). The geological sequence of the district is correlated with the Cretaceous of the Balkans; which is, in turn, a prolongation of the Alpine zone. Geological surveys made by G. Ralli, R. Zeiller and P. Arni3 show that the Eregli-Zonguldak formations fall into three natural divisions. Series a, The Alacaagzi in the district of that name (Fig. 2), is of the Culm stage. The strata strike generally east-west and dip about 30° south. This series appears also around Kandilli and Camli, with a steeper angle of dip, but the deposits there lack regularity. The Alacaagzi stage appears also farther east, to the south of Kozlu and Gelik. The Alacaagzi series contains 15 seams of an average thickness of 2 ½ ft. of good coal. Series b, the Kozlu, best represented in Zonguldak, Kilimli, Catalagzi, and between

Jan 1, 1944

By Martin S. Maier, H. R. Nelson

THE diffusion of metals plays an important role in many metallurgical processes, 1,2 as, for example, the formation of alloys by the annealing of mixed powders, the homogenization of segregated alloys, and the carburization of steel. Other equally important phenomena, such as recrystallization and creep, are based on the movement of like atoms. Although much is known concerning the effects of diffusion in metals, very little is known concerning the details of the physical processes involved.1,3-5 The data that should give most information concerning the processes involved in diffusion are those on the diffusion of like atoms-self-diffusion. Very little is known concerning the rates of self-diffusion of metals because before the discovery of artificial radio-activity in 1934 there was no means of detecting the movement of the diffusing atoms through the solvent metal except in the elements possessing natural radioactive isotopes-lead, thallium and bismuth. Using the induced radioactivity of the element as an indicator, atoms can now be "tagged" so that the rate of diffusion of the radioactive isotopes of an element (tagged atoms) into the stable isotopes of the same element can be measured. As the radioactive and stable isotopes of an element differ only in nuclear structure, it is quite certain that all isotopes of an element diffuse at the same rate. Two techniques have been used to measure self-diffusion. In one, a thin layer of radioactive metal is deposited on the face of the solvent metal, and the decrease in the surface activity as the radioactive atoms diffuse into the solvent metal is measured. This method has been used to determine the coefficients of self-diffusion of lead6-10 and bismuth10 using natural radioactive isotopes, and of gold11 and copper12 using artificial radioactive isotopes. In the other technique a thin layer of the radioactive metal is deposited on one face of the solvent metal, and after diffusion has occurred the specimen is cut in thin sections to obtain the concentration-penetration curve. This method has been used to determine the coefficients of self-diffusion of gold,13 zinc, 14-16 silver,17 and copper.18 The second method was used for the work described in this paper. MATERIALS The coefficients of self-diffusion were determined in two grades of polycrystalline copper and in single crystals of copper. Commercial OFHC copper was used in the form of disks I in. in diameter by 1/8 in. thick. Samples of high-purity copper described by Phillips and Skinner19 were supplied through the courtesy of the American Smelting and Refining Co. The high-purity copper rod was used without remelting by cross-rolling to a thickness of 0.075 in., from which disks 7/8 in. in diameter were cut. A good grade of bus-bar copper was used to make the single crystals.

Jan 1, 1942

By John W. Bell

IN the introduction to an excellent pamphlet, John Gross1 makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18, 19, 21, 22, 23, 24, 30. 34), concluded that a foundation for the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.1 One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur O. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 2323 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a. true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. STADLER'S HYPOTHESIS WORTHLESS It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left-the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things, that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in fine crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942