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By J. P. Ramsey

This is a description of the efforts of a research project intended to demonstrate methods of alleviating pollution from coal mine refuse piles and slurry lagoons. These are mainly derelict barren sites. Some are burning and some are vulnerable to wind erosion which causes air pollution. Some occupy valuable land near metropolitan areas. They are an integral part of the landscape of the Appalachian and Midwestern Coal Fields. They are important in the light of growing civic awareness of the great general problem of waste disposal and environmental improvement. In the V-shaped valleys of the Pocahontas Region, they continue to be piled higher and higher. In flatter topography, they tend to form broad, flat ridges. Some contain more metal forms than others and some have a minimum of metal, but weather to a fine talc, which chokes streams with a fine particle suspension. Most are burning or have burned, but burning or weathering, most all are sources of pollution to the atmosphere and to adjacent waterways. This demonstration project is being carried out at an abandoned mine near the town of Du Quoin in southern Illinois. It is jointly sponsored by the Truax-Traer Division of Consolidation Coal Company and by the Federal Water Pollution Control Administration of the Department of the Interior. The site area is a refuse pile and slurry lagoon, each of fifty acres. It is hoped that basic data from this study will be generally applicable to other sites and will provide a basis for rational and efficient engineering design of future reclamation projects. Most refuse piles have extremely long term capabilities to produce highly potent acidogenic oxidation products typifying the more serious aspects of acid mine drainage contamination. Numerous sites remain where the abandoned mine no longer discharges acid waters, but its associated refuse pile continues to generate significant quantities of acid and other oxidation products even after many years.

Jan 1, 1969

By D. N. Dietz

Jan 1, 1969

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By Robert G. Lundquist

The Bureau of Mines compared longitudinal strain energy output of a percussive drill to energy determined by measuring maximum piston velocity. Strain gages were used to determine the strain-time waveform and its amplitude at seven levels of operating pressure and eight levels of thrust. The longitudinal strain energy was found to be approximately 14 ft lb less than the maximum piston energy at comparable operating conditions.

Jan 1, 1969

By Darwin Soler

This chapter will outline the operating procedures at Freeport Kaolin Co.5 kaolin mining operations in Georgia, with emphasis on explaining new techniques recently introduced to reclaim mined-out areas for reforestation. Kaolin is found in the central Georgia area (See Fig. 1) in lenticular, sedimentary deposits of high purity. The beds are Cretaceous in age and vary from 4 to 60 ft in thickness, under a cover of sedimentary overburden ranging from 5 to 150 ft. The kaolin beds contain the mineral kaolinite (a hydrous aluminum silicate) and have a particle-size distribution ranging from about 20µ to the submicron level and averaging about 60% below 2µ. The only contaminants in the deposits are coarse mica, quartz particles, and minor amounts of iron and titanium oxides. These kaolin deposits vary widely in quality from deposit to deposit and also vary within individual deposits. Some of the controlling quality specifications which are determined during exploration are viscosity in water suspension, optical brightness index as measured by reflectance, amenability to bleaching, and particle-size distribution. For this reason, only a small portion of the total kaolin reserves in the Georgia belt are suitable for wet processing for the present markets being served. Kaolin clays are selectively mined by different mechanical methods and are beneficiated by both wet and dry processing to produce a number of products used as fillers and coatings in the paper industry; fillers or additives in the paint, plastic, and rubber industries; and as basic raw materials for the ceramic industry. The State of Georgia is the largest kaolin producer in the United States, with 3,206,454 tons produced in 1966, according to U.S. Bureau of Mines statistics. Freeport Kaolin Co’s processing plant is located in Gordon, Ga., about 20 miles east of Macon, Ga.

Jan 1, 1969

Jan 1, 1969

By J. A. Beesley

This paper reviews contemporary international law concerning the seabed, current developments in the United Nations on the seabed, and the main outstanding problems. It emphasizes the importance that the Canadian government attaches to this area.

Jan 1, 1969

Jan 1, 1969

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By J. D. Hadden

The Bureau of Mines conducted drilling studies in the Pocahontas No. 3, the Pittsburgh, and a western coalbed to establish the gas migration characteristics for each. Gas pressures in the Pittsburgh coalbed were about 260 lb/in2 and in excess of 550 lb/in2 in the Pocahontas No. 3. Caving in drill holes prevented pressure measurements in the western coalbed. The Pittsburgh coalbed contained intersecting "clay veins" which formed gas pressure cells. Although these geological features hamper mining, they can be used to control the flow of methane into a mine working. Methane control techniques are proposed for the Pittsburgh and Pocahontas No. 3 coalbeds.

Jan 1, 1969

By N. R. Zehr

El presente texto describe los problemas de desague y ventilación que corresponden al túnel Graton en Casapalca. En ese sentido, Antonio Raimondi menciona que probablemente fue Gratón, el primer túnel de desagüe en Casapalca: «la veta de San Antonio es drenada mediante túnel socavado hace poco tiempo y recientemente terminado. Esta conecta con áreas de trabajo situadas por debajo de las ya inundadas de modo que, para efectuar el desagüe, solo tendrá qµe perforarse en plano inclinado. Los túneles Graton tendrán poco más de 11 km, los cuales pueden perforarse desde accesos en el Valle del Río Rimac, poco más arriba del pueblo de San Mateo, en un punto denominado "Carbonyacúpalabra" quichua que significa «agua de carbón». Asimismo, estos túneles gemelos se terminarán bajo el pozo de la mina Aguas Calientes de Casapalca. Una vez terminado, una perforación servirá para desaguar las áreas de trabajo y la otra, para la respectiva ventilación.

Jan 1, 1969

The copper-clay deposits consist largely of goethite and clayey mudstones carrying native copper, cuprite, and chalcocite. The mudstones are of Ordovician age, are interbedded with Fe-Mn carbonates, and probably contained syngenetic iron and copper sulphides. The secondary copper minerals have been derived from post-Devonian weathering in situ and also by deposition from surfaee and underground waters draining the adjacent mineralized volcanic rocks.

Jan 1, 1969

By John C. MacCartney

In the Pennsylvania anthracite region, the principal source of U.S. anthracite, refuse disposal problems are common since cities and towns are located over the anthracite measures. The Bureau of Mines surveyed refuse banks in the area, determining that 863 banks containing aver 910 million cubic yards of material occupy a total area of about 19 square miles. The vast bulk of the refuse is located within 2 miles of the traffic centers of incorporated c unities which have a total population of 625,000. Twenty-seven banks are burning, causing considerable distress in a number of communities.

Jan 1, 1969

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By P. R. Jones

The Bureau of Mines has written a computer program for the design and cost of a shell and tube type heat exchanger, in which a change in phase occurs on the shell side. The total cost, which was minimized, includes the annual fixed charges and annual operating costs. The program was written to meet the following requirements: (1) Triangular pitch, (2) single or multiple pass, and (3) heating or cooling. Price optimum design was obtained for four standard tube diameters and pitch. Standard heat exchangers whose area equaled or exceeded the required area are also listed. The program was made adaptable to various fluids and to various tube dimensions by including many of the required data such as physical properties of the fluids, tube data, and standard shell data as input data.

Jan 1, 1969

By C. L. Magee, H. W. Paxton

PREVIOUS workersl'% ave found that as-quenched ferrous martensites can be plastically deformed at low stresses. They have also found that the stress to obtain small strains can be significantly increased by aging at temperatures up to 150°C. This behavior has been interpreted in two ways: 1) that the deformation at low applied stress is due to internal stresses and thus the aging phenomenon is due to relaxation of the internal stresses;' 2) that the microdeformation arises through the motion of unpinned dislocations and the aging process is the diffusion of carbon to the dislocations to pin them.293 In a recent paper,4 we have shown that under certain conditions the dominant microdeformation mechanism of as-quenched Fe-31Ni marten-site-austenite aggregates is the transformation of retained austenite. Our results on resistance changes during deformation and temperature dependence of the deformation also established that, at temperatures above 300° K, the microdeformation was not due to this transformation. The purpose of this note is to report results of experiments which indicate that explanation 1 is appropriate for this deformation. All results presented here are from conditions where transformation does not make a measurable contribution to the microplastic deformation, in Fe-31Ni-0.002C, or in Fe-29Ni-0.02C-0.25Ti. The experimental techniques that were used for measurement of the plastic deformation are described4 and analyzed5 elsewhere. Fig. 1 shows the microplastic response of 100 pct austenite at 300" and 350° K. The microplastic response of an austenite-martensite aggregate is also given in Fig. 1 and it is seen that, after formation of martensite, the initial plastic deformation occurs at lower stresses. Thus, the softness is not entirely due to retained austenite—the quenched structure can be deformed at lower stresses despite the fact that the macroscopic strength is significantly higher. A result which allows a distinction to be drawn between the alternative explanations for this behavior is derived from aging experiments on the low-carbon alloy containing titanium. We have previously shown4 that the presence of titanium in this alloy reduced the free carbon to a sufficiently low level that thermal stabilization of the austenite-martensite transformation was not detected. Despite this, Fig. 2 shows that the microplastic response is decreased by aging treatments. A similar aging effect in Fe-ZONi, with some titanium, has previously been reported by . Thus, carbon is not necessary for the aging process and explanation 2 is at best incomplete. Since internal stress relief can occur independently of carbon (any temperature dependence of the flow stress can result in decreased internal

Jan 1, 1969

Using a Jarrell-Ash "Compact" direct reading spectrometer, analyses were made of a wide variety of rocks ranging from acidic to ultrabasic types. Statistical evaluation suggests that accuracies comparable with the values obtained by the rapid chemical methods used by the United States Geological Survey will be obtained.The spectrographic method involves fusion of the rock with lithium tetraborate, strontium being incorporated in the flux as the internal standard. The resulting bead is ground with graphite and pressed into a pellet. The counts obtained on two standard pellets are used to correct for instrumental drift.Background readings are made at 4109 Å and corrections for background are made to all lines. Corrections for matrix interferences, both by chemical suppression and optical enhancement, are made. The three corrections of drift, background, and matrix are incorporated into one general expression which has been programmed on magnetic cards, each element requiring a separate card. The cards are placed individually into a desk top computer (an Olivetti Programma 101), which enables true counts to be calculated from the "readout" counts, and the element concentration is then obtained from computer-printed tables by referring to the appropriate value of true counts versus concentration. These tables were prepared by making a polynomial regression analysis of the spectrographic results from 50 standard and analysed samples, a curve of best fit being chosen for each element.The regression coefficients, usually of a fourth or fifth degree equation, together with other relevant data, were fed into a large computer, programmed to print out tables of concentration versus true counts. This technique enables the results obtained to be based on mathematically-derived values rather than on hand-drawn calibration graphs, giving greater inherent accuracy. The technique has been shown to give results of good accuracy and acceptable precision suitable for many geological and geochemical exploration programmes involving the analysis of many rock samples of different types.

Jan 1, 1969

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By R. A. Burton, J. T. Hansford, D. A. T. Donohue

Substantial evidence indicates that many petroleum producing horizons contain naturally occurring, ordered fracture systems and that within a particular geologic zone, vertical fractures induced in wellbores often will be directed along a particular compass direction. Both conditions will seriously alter the fluid displacement behavior within reservoirs. In this study the effect of induced fracture orientation and length on sweep efficiency is determined for a five-spot pattern. In general, it is assumed that all wells are fractured and directed along the same compass direction. Using the electrical analog to steady state, two-dimensional fluid flow in porous media, boundary conditions are obtained from which flood fronts are tracked numerically. The numerical computations require a particle tracking routine for approximating flood front histories. It is shown that recovery is sensitive to the length and orientation of fractures for the pattern studied. with the proper design of fracture-pattern systems, recovery can be enhanced considerably. INTRODUCTION Hydraulic fracturing introduced in 1949l gave the industry a rather inexpensive means of increasing the fluid injection or production capacity of wells. It has been used with particular success to increase the production rate of wells completed in tight formations, such as in western pennsylvania2 where producers have fractured in depleted or near-depleted fields and observed economic responses. Once the natural energy declines in such a reservoir where all wells have been fractured, waterflooding is generally suggested as means of further increasing recovery. Of the dual objective sought in waterflooding — high injectivity and high breakthrough sweep efficiency — the former condition can be obtained if all wells in the flood pattern are fractured; the latter condition should depend on the nature of the fracture system. Considerable theoretical work has been published on the nature of fractures induced in boreholes.3-5 Although discussion persists concerning the possibility of forming a horizontal fracture at a given point within the wellbore, it is generally conceded that only vertical fractures will develop below a given depth, i.e., where the fracturing Pressure is less than the overburden load. Given the fact that fractures will be vertical in most cases of interest, it is also important to know whether there is order to fracture orientations within a given geological region. Kehle has suggested that in tectonically relaxed areas of uncomplicated geology, the stresses are fairly uniform and all fractures in the region should be parallel.5 Dunlap arrived at a similar conclusion in a theoretical investigation of localized stress conditions surrounding the borehole.6 He concluded that most vertical fractures are propagated in a preferred azimuthal direction. Fraser and Pettitt, in extending these theoretical suggestions to a specific field case, used an impression packer to record both a vertical fracture and the orientation of this fracture in the wellbore of a well in the Howard Glasscock field, Tex.7 Use of this information enhanced the waterflood recovery of the field. Anderson and Stahl also used impression packers on three fractured wells in the Allegheny field. N. Y.. and found that the fractures were oriented more or less along the same compass direction.8 Orientation of the fractures in this manner depends on the stress condition within the formation during fracturing. Elkins and Skov have demonstrated that a natural, oriented, vertical fracture system exists within the Spraberry field? Heck suggests

Jan 1, 1969

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969