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By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By Stephen Burke

THE oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combus-tion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the condi-tions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 21120 + 702 --> 2FeSO4 + 2H2S04 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to dis-close any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1937

By G. H. Pardue, L. H. Gollwitzer, J. H. Moran, R. L. Morris

Experimental and theoretical studies of casing-borne signals have provided data on the attenuation efect, compressive strength and shear modulus for different types of cement. These data resulted in the establishment of a definite relationship between the cement compressive strength and the Cement Bond log reading. The relationship is influenced by the casing dimensions, but is independent of the type of cement and the curing conditions. The theoretical analysis provides a mathematical statement of the phenomenon and shows that the attenuation rate is basically a function of the shear modulus of the cement and the thickness of the casing. The lab tests provided a connection between the shear modulus and the compressive strength, and permitted a comparison of the experimental and theoretical work. The results of the experimental and theoretical study have provided means of quantitative interpretation of the Cement Bond log. This interpretation is made more convenient with the use of a nomograph. INTRODUCTION Past interpretation of Cement Bond logs has been essenlially based upon a qualitative comparison between the log response in the zone of interest and the responses in the "fully cemented" and the "uncemented" intervals. Most of the variables influencing the magnitude of the signals were recognized in an earlier paper'; however, insufficient laboratory data were available at that time for quantitative evaluation of these variables. Early attempts to use the numerical amplitudes of the signals without full knowledge of their significance resulted in erroneous comparisons between various types of cement. An extensive program was undertaken to evaluate, both experimentally and theoretically, the attenuation phenomenon and to study the effects of the more common variables. A major objective of the experimental program was to obtain data on the relationship between cement-bond-tool response and physical property standards used by the industry so that practical interpretation methods could be devised. The studies included a comparison of attenuation rate with these properties as a function of time, temperature and pressure, using common sizes of casing. The main result was that a definite relationship was established between the compressive strength of the cement in inti- mate contact with the casing and the response of the cement bond tool. For a given casing thickness, regardless of the type of cement or the curing conditions used, the attenuation rate is a function of the compressive strength. A theoretical analysis showed that the attenuation rate for casing-borne signals should be a function of (among other things) the shear modulus of the cement and the thickness of the casing. The relationship between the compressive strength and shear modulus for curing times similar to those encountered in the field was determined from laboratory tests. Using this relationship, the computed attenuation rates showed reasonable agreement with the measured attenuation rates. The purpose of this paper is to report the results of the experimental and theoretical investigations and to present the first practical method for a quantitative interpretation of Cement Bond logs based on known variables. This method is applicable where the casing-borne signal is not affected by high-velocity formation arrivals. DESCRIPTION OF LOGGING TOOL The Cement Bond logging tool shown schematically in Fig. 1 has been described previously.' The tool consists of two sections: acoustic and electronic. The acoustic section contains a transmitter and a receiver, usually spaced 3-ft apart. Sonic energy emittted by the transmitter travels through the casing and is detected at the receiver. The electronic section measures the amplitude of the

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.' Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By Francis H. Brownell

During the 1920's lead consumption in the United States reached the highest average total ever known. For the ten-year period 1921-'30, it was slightly over 600,000 tons per year, or say 50,000 tons per month, and the price averaged 6.81 per lb. But the I930's witnessed a severe drop in the consumption of lead is in other business activities. The average U.S. consumption for the ten-year period 1930-'40 was slightly less than 380,000 tons per year, or under 32,000 per month, with the average price dropping to 1.191c. per lb. The outlook in early 1939 was for a continuation of this average consumption and price a demand of 35,000 to 40,000 tons per month, and a price level of 4 1/2 to 5c. in the United States.

Jan 1, 1941

By C. C. Miller, C. A. Hutchinson, A. B. Dyes

This paper presents a simple and practical method for the estimation of effective permeability and reservoir pressures from the rise in bottom hole pressure when a well is shut in. The equations on which the method is based consider a stabilized well producing from a uniform formation when flow is shut off at the sand face followed by the unsteady state flow of a compressible liquid from regions far from a well to points closer in during the build-up period. An approximation for extending the method for two-phase flow in the reservoir is also presented. In order to compare the effects of extremes in the conditions existing at the external boundary of the reservoir, two general equations defining the build-up characteristics of the reservoir are shown: first, for a reservoir with constant pressure maintained at the radius of drainage, and second, for a reservoir with no influx over the radius of drainage. These equations define the build-up characteristics for the shut-in well as functions of time, the permeability and porosity of the drainage area, the viscosity and compressibility of the fluid flowing, the production rate prior to shut-in, and the radius of drainage of the well. When a well is shut in at the surface, rather than at the sand face, flow will continue into the well bore after shut-in due to the compressibility of the fluids in the bore. The effect upon the build-up characteristics of this flow into the well after shut-in has been studied by means of the electrical analyzer. From the basic relationships and consideration of the limitations due to continued flow after shut-in, methods have been developed for the estimation of the effective permeability of an area from the plot of the build-up characteristics of the well producing that area. Likewise, equations are presented for the estimation of the reservoir pressure from an early portion of the build-up curve. By means of the electrical analyzer, studies have been made concerning the variations in the build-up characteristics resulting from damaged or improved permeability in the immediate vicinity of the well bore. These studies show that the permeability estimated from the build-up curves represents the average effective permeability of the majority of the drainage area and that the permeability in the immediate vicinity of the well does not affect this estimate. Since the major portion of the drawdown is in the immediate vicinity of the well, variations in the permeability of this area greatly affect the productivity of the well as expressed by the productivity index. From pressure build-up and productivity index tests the ratio of the permeability of some arbitrarily specified area immediately surrounding the well and the effective permeability in the majority of the drainage area can be computed. This ratio is a measure of any damage to the well incurred in drilling or reworking and likewise any benefits as a result of remedial measures. In build-up tests and many other tests that are made on a producing well it is at least desirable, if not absolutely necessary, that the well be stabilized prior to testing. A method is presented here for relating the time required to stabilize a well and the reservoir and fluid properties. An equation is also presented for approximation of the length of shut-in time required to obtain sufficient build-up data for the estimation of permeability and reservoir pressure.

Jan 1, 1950

By H. Schwartzbart, J. R. Low

Annealed, .Poly crystalline, low carbon steel exhibits a phenomenon known as the "yield point." If such a steel is loaded in tension, the load increases steadily with elastic strain, drops suddenly, fluctuates about some constant load value for a time and then rises with further strain. The load at which the sudden drop occurs is called the "upper yield point"; the load at which deformation proceeds at constant load is known as the "lower yield point"; the amount of elongation at constant load is termed the "yield point elongation." Deformation which occurs during the yield point elongation is heterogeneous in nature, deformed metal existing next to undeformed metal. The drop in load from the upper yield point is concurrent with the formation of a band of deformed metal which usually appears at a stress concentration such as a fillet and at an angle of approximately 45" with the direction of pull. As deformation proceeds during the yield point elongation, the deformed region grows until the entire specimen has been strained an amount equal to the strain in the first band. A phenomenon very often associated with the yield point is that of strain aging. Aging in steels may be of two types: quench aging, or precipitation hardening, and strain-aging. Strain aging differs from precipitation hardening in that if the metal is merely strained instead of given a solution anneal and quenched, it then undergoes changes in properties similar to those observed in quench aging. The yield point effect and strain aging are most markedly exhibited by low carbon steel, but have been observed in other alloys. Numerous explanations for the mechanisms of both phenomena have been advanced, but the evidence for the acceptance of any of the hypotheses is incomplete. One of the explanations of the yield point phenomenon frequently proposed is that there exists a honeycomb of grain boundary material that supports the load above the yield strength of the ferrite and that when this network ruptures, the ferrite flows with no increase in load. This notion was first advanced by Dalbyl in 1913 and has been since put forward in more concrete form by many investigators. The testing of this hypothesis was, in part, the object of the present investigation. Similarly, the mechanism by which strain aging occurs remains to be explained. Presumably, it is a precipitation hardening phenomenon similar to quench aging, the precipitation being initiated by strain. However, it is not known whether the process is a solution and precipitation effect or a change in solubility due to strain. One obvious method of determining whether or not the yield point is a grain boundary phenomenon is to determine if single crystals exhibit a yield point. Low and Gensamer2 have shown that carbon and nitrogen are responsible for the yield point and aging in steel and that these effects can be eliminated by the removal of these elements through wet hydrogen purification. Single crystals that have been grown in wet hydrogen treated material must then be recarburized or re-nitrided in order to evaluate the effect of grain boundaries. In the present investigation, single crystals of iron which had been annealed in wet hydrogen to remove the carbon and nitrogen were cut into two specimens having the same orientation with respect to the tension axis. Of these, one specimen was pulled in tension in the wet hydrogen treated state and the other was carburized or nitrided and tested similarly. All the crystals were examined for a yield-point and strain aging. The grain boundary hypothesis for the explanation of the yield point in steel has been tested only indirectly previously. Arrowsmith,3 Andrew and Lee,4 Edwards and Pfeil,5 Fell,6 Ludwik and Scheu,7 Winlock and Leiter8 and others found a decrease in proportional limit and yield point effect with an in-

Jan 1, 1950

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By Walter E. Duncan, Oscar F. Tangel, A. M. Gaudin, Franklin Dewey, R. A. Johnson

Xanthates have been used as collectors of sulfide minerals in the concentration of ores by flotation for over a decade, yet much remains to be done to elucidate the underlying reasons for the remarkable effectiveness of these compounds in this connection. Briefly stated, the known facts concerning the effect of these reagents on the floatability of minerals are as follows: 1. Xanthates are without effect on silicates, silica, and generally on minerals currently regarded as "gangues." 2. Xanthates in very small amount increase enormously the floatability of sulfides of copper, lead, silver, iron and mercury. 3. If zinc sulfides are first '(activated," as by treatment with a copper salt, they are readily floated by xanthates; otherwise not. 4. Elemental copper, silver and gold have their floatabilities increased by xanthates. 5. Sulfides of elements that are not typically metallic—e.g., stibnite, realgar, molybdenit—are not made to float markedly better by treatment with xanthates. 6. Oxidized minerals of lead and copper are floated if treated with large amounts of xanthates, but not so if treated with amounts of the same order of magnitude as required for sulfide flotation. Oxidized zinc minerals are not floated unless xanthates having unusually long hydrocarbon chains (e.g., eight carbon atoms or more) are used. Iron oxides and carbonate are not floated by xanthates. From a flotation standpoint the most striking feature about xanthates is the very small amount required to accomplish startling changes in the behavior of some minerals. The amounts used in practice to effect excellent concentration are frequently of the order of 0.05 lb, of agent per ton of ore; that is, of the order of one part of agent per forty thousand parts of ore. Changes in amount of agent of the order of 0.01 lb. per ton of ore (or 0.002 lb. per ton of pulp, on a 4:l basis) have marked effects on the metallurgical results obtained. Yet these changes represent a variation of but one part per million parts of pulp.

Jan 1, 1935

By C. W. Washburne

Recently, Messrs, Mills and Wells1 published a thorough chemical study of the waters associated with oil in parts of the Pennsylvania, Ohio, and West Virginia region. Many of their conclusions are of general application and the writer wishes to discuss some of these. Messrs. Mills and Wells show that the composition of the deep brines oi the Appalachian fields is such as would be produced by the evaporation of sea water and the precipitation of sodium chloride, combined with reactions with hydrocarbons and other substances. The brines are altered, also, by considerable mixing with meteoric water. They give good reasons for believing that the concentration of the brines was produced by evaporation in the rock pores induced by migrating gas, much of which probably escaped to the surface of the ground. This hypothesis was considered by the writer in a former paperJ2 in which main stress was laid on a second hypothesis, that the excess of chlorine in the deep brines may have been due to the entrance of solutions rich in magnesium and calcium chloride which ascended from a deep, possibly intratellurie, source. Messrs. Mills and Wells present good arguments for the first hypothesis. Underground evaporation by ascending gases probably will be accepted as the best available explanation of the concentration and composition of deep well waters. They have not considered the possibility that salt waters in deep sands may be concentrated by the diffusion of water vapor through gas into shale. The writer has given reasons3 for believing that capillary forces concentrate gas and oil in the larger openings of rock, such as the pores of sandstones embedded in shale. The gas underground must be nearly saturated with water vapor at all times, because it always is in contact with the interstitial water of enclosing shales and of the sandstone. Experimental studies of soil moisture have shown that approxi-

Jan 1, 1921

By C. B. Daellenbach, T. D. Tiemann

The prevention of quartz flotation by chelation of activating ions with the tetrasodium salt of EDTA in oleic acid flotation was investigated using a small vacuum flotation cell. It was found that flotation of quartz could be entirely suppressed in the presence of activating ions during complete flotation of hematite. It was further shown that the concentration of activating ions liberated from Wisconsin Gogebic taconite is sufficient to float quartz in an oleic acid system. Large tonnages of low grade siliceous iron ores occur on the iron ranges of the Lake Superior district. Although the lower grade nonmagnetic types are currently not of economic importance, they constitute a large future potential source of iron and steel, and hence have been the subject for extensive research on their beneficiation. TACONITES Of particular interest to the Dept. of Minerals and Metals Engineering at the University of Wisconsin have been the low grade nonmagnetic taconites of the Wisconsin Gogebic Range. These occur as five members of the iron formation and have been described in detail elsewhere.' Essentially they consist of an intimate mixture of hematite, goethite and quartz, with minor amounts of siderite, magnetite, iron containing silicates, and manganese minerals. A typical mean analysis based on the Bureau of Mines analyses' is: SiO2-52.50%, Fe2O3-43.40%, (Fe-30.38%), A12O3-1.15%, P2O5-0.07%, Mn2O3-0.29%, CaO-0.07%, (S-0.03%), Loss on ignition-2.00%. The quartz in these ores is of a microcrystalline variety,2 and so intimately associated with the iron oxide minerals that extremely fine grinding, in the order of minus 325 mesh, is required for liberation. During grinding and subsequent flotation, the concentration of quartz activating ions in the pulp becomes sufficiently high to activate quartz which floats along with the iron minerals in the presence of oleic acid. cook3 and co-workers concluded that oxidized iron ores released appreciable quantities of quartz-activating ions in water pulps. This is shown to be true in the present investigation. As a matter of fact, application of this phenomenon, as well as the intentional addition of activating calcium ions, is made use of in the an ionic flotation of silica from the iron oxide minerals.4,5 In view of the above, it becomes almost impossible to effect a sharp separation of quartz in the oleic acid flotation of the iron oxide minerals from these taconites, even with satisfactory liberation. This fact led to the current investigation to find a means of linking the activating ions with a chelating agent. The aim was to establish basic data for the quartz-water-oleic acid system which might not only be applicable to iron ores, but also to the flotation of other siliceous ores as well. EXPERIMENTAL METHODS Vacuum Flotation Cell: The vacuum flotation used in this investigation is similar to that used by previous investigators.6,7,8 The cell consisted of a 100 ml graduated cylinder with the lip removed. Vacuum from a water aspirator was applied to the cell through a trap; suitable tubing, and a rubber stopper inserted in the top of the cell. Constant absolute pressure was maintained by means of a manometer connected to the trap with a tee. Flotation: The required amount of activating ion solution was pipetted into a beaker. This was then diluted to 99.0 ml with water having a pH below that desired for the test, or so adjusted with HC1. After addition of 1.0 ml of oleic acid solution (2.0 mg oleic acid per ml), the pH was readjusted to the desired value with NaOH, and the entire solution transferred to the cell containing 1.5 gm of quartz. After vigorously agitating the cell and its contents for 2 min, the vacuum was applied to the cell and the estimated degree of flotation observed for a 3-min period. Activating ions studied included Ca++, Mg++, Al+++, and Fe+ + + added as chloride solutions. In addition,

Jan 1, 1964

By F. O. Jones

The capabilities of small proportions of divalent cations, such as calcium or magnesium, for controlling clay blocking are reported. Potentially sensitive formations can be exposed to fresh water if at least one-tenth of the salts dissolved in both the native water and invading fresh water are calcium and magnesium salts. Often, even less suffices. The behavior evidently depends upon the cation exchange properties of the clays, which favor adsorption of calcium and magnesium over sodium. Clays having sufficient adsorbed calcium and magnesium resist dispersion by water and consequent blocking of permeability. An allied phenomenon, the dependency of clay blocking on salinity contrast, is also reported. Abrupt change from highly saline to fresh water can cause blocking which may not occur if salinity is lowered slowly. A process related to osmosis is thought responsible for this behavior. Applications of findings to drilling, fracturing and water flooding are discussed. INTRODUCTION Many formations, when exposed to fresh water, can lose permeability through clay effects.',' For example, drilling-mud filtrate can cause oil permeability decreases, which persist long enough to interfere with drill-stem testing and well completion.3 Ultimate productivity may suffer when clay damage is severe, especially if drawdown pressures are low.' The injection pressures and the time required for water flooding can increase if clay blocking occurs. Earlier work indicates that clay blocking is caused by obstruction of flow channels by clays or other mineral fines dispersed by fresh water.'!" It is well known that increasing salt concentrations in water tends to prevent clay blocking. Also it is well established, although perhaps not as widely known, that the nature of the dissolved solids is also important. If, for instance, formation clays are exposed to calcium chloride solution and then exposed to weaker solutions of calcium chloride or distilled water, considerably less permeability damage results than if the clays had been exposed instead to sodium chloride solutions. The reasons for this behavior are: (1) clays are cation-exchange, or base-exchange, materials similar in this respect to zeolites or exchange resins, and (2) clays in the calcium form do not disperse easily in fresh water, whereas clays in the sodium form do. The base-exchange form of a clay is easily altered by flowing a solution through it. For example, a sodium clay can be changed to a calcium clay simply by passing a calcium chloride solution through the clay bed. There is general agreement that the reason calcium and magnesium clays do not disperse easily in fresh water is because the calcium ions do not ionize easily from the clay surfaces.' Sodium clays, however, are believed to allow the sodium ions to ionize from the clay particle surfaces. In fresh water, this allows the particle to accumulate a net negative electrical charge great enough for the particles to repel one another and, therefore, disperse more easily. The foregoing suggests that, even in the presence of a large excess of sodium, a relatively small ratio of divalent cation, such as calcium or magnesium, might serve to prevent clay dispersion. The divalent ion probably adsorbs to a disproportionately large extent, because of being adsorbed more tightly, with the result that the proportion of divalent cation on the exchange positions of the clay might then be great enough for the clays to resist dispersion. Consequently, an investigation was conducted to find how mixtures of salts in solution influence clay blocking. APPARATUS AND PROCEDURE Water permeability tests were conducted using conventional techniques. The equipment is illustrated schematically in Fig. 1. Flow rates of solutions driven through small core samples at known temperatures and pressures were measured. Regulated compressed air, usually at 10 to 15 psig, was used to drive the solutions. Core samples 0.75 in. in diameter and 1 in. long were used for the most part. Cores were saturated by evacuating and then admitting a de-aerated solution. Tight core samples were first saturated with carbon dioxide gas and then evacuated and saturated with the test solution. After saturation, 140 psig pressure was imposed for several hours. Cores were tested to insure absence of gas saturation by a Boyle's

Jan 1, 1965

By E. W. Johnson, M. L. Hill

Equilibrium concentrations of hydrogen in iron were measured at H2 pressures up to 136 atm and temperatures down to 145°C. Residual hydrogen was prominent near 600°C in air-melted but not in vacuum-melted iron. The diffusible hydrogen solubility is abnormally high below 390°C, confirming the hypothesis of hydrogen trapping.' It appears that the traps for hydrogen in iron form suddenly on cooling. The estimated H2 pressure in equilibrium with 5 ppm hydrogen in steel at room temperature is less than 1000 atm. It was shown previously1 that the diffusivity of hydrogen in a-Fe below 200°C is anomalously low, a behavior attributed to the presence in the metal structure of hydrogen "traps." The energy of the trapped hydrogen was computed as 4.8 kcal Per g-atom below that of the interstitially dissolved hydrogen. The strongest confirmation of the trap hypothesis should be obtainable from measurements of the hydrogen solubility at low temperatures. such measurements have been performed and are reported in this paper. The "residual hydrogen" effect1'' must be carefully controlled if valid measurements of the solubility are to be obtained, and such an effort was made in the present work. Previous data for the solubility of hydrogen in iron have been summarized by Geller and Sun.3 Their equation for the most probable solubility at 1 atm in a-Fe above 400°C is

Jan 1, 1962

By J. C. Wilhoit, E. M. Galle

A three-dimensional photoelastic study was made to determine the stress state around the wall and bottom of a wellbore due to fluid pressure within the wellbore and unequal principal geostatic stresses. Models simulating the wellbore were made from a phthalic anhydride-cured epoxy resin. The frozen stress technique of three-dimensional photoelastic-ity was used to determine the stresses within the model. Two separate problems were solved: (1) hydrostatic pressure on all sides of the model with the exception of the inside of the hole, and (2) uniaxial compression perpendicular to the center line of the hole. The results are presented in the form of contour curves for each stress component. The curves cover a region which extends several hole radii from the bottom and wall of the hole. By proper use of these results, the state of stress may be calculated for any point on the wall or bottom of the hole, as well as for any point within the material that surrounds the hole. A systematic method is given for calculating these stress components for any combination of fluid pressure within the wellbore and system of unequal principal geostatic stresses, provided one of the principal geostatic stresses is parallel with the wellbore. The results show that stresses around the wall and bottom of a wellbore, induced by an uneyual system of principal geostatic stresses, are appreciably different from those induced by geostatic stresses that are hydrostatic. For uneyual principal geostatic stresses, the experimentally determined stresses on the wall of the hole several radii from the bottom are in good agreement with the stresses calculated by elastic theory. INTRODUCTION Interest in the problem of determining the stresses around and near the bottom of a wellbore, due to geostatic loading and fluid pressure within the wellbore, originated in the petroleum industry. The stresses on the wall of the wellbore are of interest due to their relation to lost circulation during drilling, the fracturing of formations during squeeze cementing and hydraulic fracturing of producing formations. The stresses on the bottom of the hole are of interest to the drilling segment of the industry because to produce a hole in the earth it is necessary to remove material from the bottom of the hole. This removal of material is produced by structural failure of the rock, whatever the criterion for failure may be. Cunningham and Eeninkl have shown that for certain conditions the effect on drilling rate of the bottom-hole stresses caused by a hydrostatic overburden pressure is small compared to other effects. This question, however, needs further experimental and analytical investigation. Much information concerning the stresses on the walls of wellbores has been published considering both equal and unequal principal geostatic stresses. The problem of determining the stresses around the bottom of the wellbore is considerably more complicated. However, previous investigators have obtained numerical and experimental solutions to the problem for equal principal geostatic stresses. whitworth2 and woods3 have obtained numerical solutions. word415 obtained a three-dimensional photoelastic solution, Durelli and Deily 6 obtained surface stresses only by photoelastic means, and Cheatham and Wilhoit7 determined the stresses around the bottom of a short cylindrical cavity. While Miles and McGuire, Harrison and Kieschnick and Hubbert and Willis 10 obtained the stresses on the wall of a wellbore for unequal principal geostatic stresses, they did not concern themselves with the stresses near the bottom of the hole. The estimates made by Hubbert and Willis of the differences between the principal geostatic stresses indicate that, to obtain a satisfactory solution for the stresses around the bottom of a wellbore, unequal principal geostatic stresses should be considered. This work is directed toward obtaining such a solution. The materials in the earth's crust are nonhomo-geneous, permeable and anisotropic. Previous

By P. K. Weimer

Coinpletely integrated thin-film circuits inco?,porating more than 1000 active and passive elements have been fabricated reproducibly in the laboratory by evaporation of- all components. A 180-stage modified shift register comprising 540 CdSe TFT's, 360 resistovs, and 180 capacitors was deposited upon a glass substrate during one pump-down of the vacuum systeitl. Experimental units have been operated for more than 5000 hr at temperatures uP to 85°C without failure of any slages. The present pupper reviews the charvactevistics of evaporated thin-film transistors (TFT's) and discusses their application to integrnted circuils. INTEGRATED circuits most widely used today are based upon silicon technology, with the circuits formed on the surface of a block of single-crystal silicon1 or on a block of sapphire 2,3 upon which a thin layer of silicon has been deposited. Transistor patterns and interconnections are defined by photographic procedures using photoresist masking. Large groups of transistors are produced in batches which undergo many processing steps, some of which are carried out at elevated temperatures. Passive elements are formed by treatment of the semiconductor surface or are deposited by evaporation alongside the active elements. The size and complexity of the circuits are limited by defects in the devices and by the size of the available single-crystal chips. Capacitative coupling to the semiconducting substrate may also limit useful size and frequency response of the circuits. An alternative approach to integrated circuits is based upon the deposition by evaporation of all circuit components upon a noncrystalline, insulating substrate such as glass.4 Thin-film field-effect transistors,1'6 known as TFT's, can be deposited in large arrays on glass or plastic substrates at the same time the associated passive elements are being deposited. Although still in the research stage the all-evaporated approach is expected to offer certain advantages for many applications. In particular, the use of thin films upon a noncrystalline substrate offers the prospect of producing complex, large-area circuits not now feasible with single-crystal silicon. Important applications of this type include memory arrays for computers and imaging devices for television. The ease with which the evaporated TFT's can be deposited may permit continuous, automated production methods not possible with high-temperature batch processing. Recent advances7'8 in the fabrication of thin-film transistors have led to greatly improved reproduci-bility and life of the TFT's. Experimental circuits having over 1000 active and passive elements deposited upon a common glass substrate are currently being produced in the laboratory. The present paper reviews recent progress in the development of the TFT and in its application to integrated circuits. I) DESCRIPTION OF THE THIN-FILM FIELD-EFFECT TRANSISTOR The TFT is a field-effect transistor of the type having the control gate separated from the semiconductor by a thin insulating spacer. Although its operation resembles that of the silicon MOS transistorg its construction is based entirely on thin-film techniques. Fig. 1 shows a cross-sectional view of an evaporated TFT deposited upon a glass substrate compared with a silicon MOS transistor deposited upon single-crystal sapphire.3 The semiconductor in the TFT is a poly crystal line layer, of a material which can be readily evaporated, such as cadmium sulfide, cadmium selenide,l0 or tellurium." Silicon monoxide layers have usually served as the gate insulator, but other oxides, sulfides, and fluorides may be used. Film thicknesses range from a few hundred to a few thousand angstroms. The source, drain, and gate electrodes in the TFT are of metal. Qpical source-drain gap dimensions are 0.0003 x 0.030 in., with a gate strip whose width slightly overlaps the source and drain. The source and drain electrodes should make low impedance contacts to the semiconductor. With cadmium sulfide films, gold is a satisfactory material for underlying electrodes, while aluminum is preferable for overlying electrodes.12 Considerable variation in design of the TFT is permissible, with the electrodes being

Jan 1, 1967

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By B. K. Larkin, H. R. Bailey

One of the most complicated and potentially one of the most promising secondary recovery methods is that of underground combustion. A number of field tests1,2,3 have been performed recently, apparently indicating that the underground combustion process is technically feasible. Relatively little has been published concerning laboratory or theoretical investigations of the underground combustion process. A few results of laboratory tube runs have been published4,5 and these data are valuable in understanding the process. The tube run data also emphasize the complexity of the thermal recovery process. Under various conditions, problems in heat transfer, multiphase fluid flow and combustion rates arise. For example, at low temperatures the combustion process proceeds so slowly that the front cannot be propagated. It is a problem in heat transfer to predict what injection rate of air is necessary to sustain combustion in a particular reservoir. Certain fluid flow aspects of underground combustion have been studied by Wilson, et a13. In the development of some of the flow equations, assumptions of adiabatic combustion were made. Vogel and Krueger1 have devised an analog model of the heat conduction process for a constant temperature cylindrical source moving radially outward in a homogeneous conducting medium. Jenkins and Ramey7, in a discussion of the Vogel and Krueger paper, present an analytical solution of a heat conduction problem related to problems considered by Vogel and Krueger. In the present paper an idealized model of the heat conduction problem is considered, which is more general than the model of Vogel and Krueger or Jenkins and Ramey. In particular, initial well heating, vertical heat losses and arbitrary frontal velocities are included. Equations for the temperature are obtained in terms of integrals. These integrals have been evaluated numerically for the case of frontal movement corresponding to a constant air injection rate and the case of constant frontal velocity. These results are presented graphically. From these graphs one may estimate conditions under which nearly adiabatic temperatures are obtained. The application of these results requires some knowledge of reservoir thermal properties, combustion rates and residual fuel content. Assuming no vertical losses it is possible to obtain explicit evaluations of these integrals in the linear con- stant velocity case and in the radial case corresponding to a constant air injection rate. PRESENTATION OF RESULTS The geometry of the radial system is illustrated in Fig. 1 where the reservoir is represented as a slab of thickness h. By making an energy balance for an infinitesimal volume, one obtains the following equation. T= x T+F(z.r).........(1) where F (z,r) =HWv1/pc (r-r1), if z h/2 = 0, if z >h/2 . In Eq. 1, V- represents the Laplacian operator and 8 is the Dirac delta function. Eq. 1 is the well-known diff-sion equation with a source term and may be applied to a linear system. For example, if the source is moving in the direction of the x axis, then the argument of the delta function is x - 1,. In deriving Eq. 1 the following approximations were made concerning the actual combustion process: (1) all heat transfer is by conduction in a homogeneous medium, (2) the formations bounding the reservoir have the same thermal properties as the reservoir, (3) the combustion fuel is consumed instantaneously as the front arrives, (4) there is a constant fuel concentration

By Joseph B. Perry, G. M. Kirwan

MAGNESITE is found in 22 California counties, but many of the deposits are too small or too impure to be of commercial value. Several of substantial size and quality were entirely exhausted by wartime operation. At present, three properties comprise the only known workable deposits in the state. Of these, the Western mine and the Patterson mine have been known and worked for many years, and have been described in considerable detail in various publications, therefore need only brief mention here, because of their proximity to the Bald Eagle mine. The latter, recently developed, is unusual in type of ore deposit, plant design and operation, as well as products made, and very little has been written concerning it. WESTERN MINE The Western mine, 32 miles south of Livermore, Calif., was formerly operated by C. S. Maltby. It has been a consistent producer for many years.1 The ore is of amorphous variety, occurring along fracture zones in serpentine. The veins vary greatly in width, the average being perhaps 8 ft., with the maximum indicated in one early stope of 40 ft.; 2 ft. is considered the minimum for economical mining. The strike of the veins is predominantly north and south, with dip to the west varying from 40º to 75 º. Walls are well defined and as a rule firm and easily supported. Veins range in length from a few hundred feet to 1000 or more. Their maximum vertical extent is about 350 ft., but many run less. Early mining consisted of open-cut and glory-hole work on the larger outcrops. This was followed underground by a modified shrinkage system, the waste and low-grade horses being removed by hand sorting on the tramming levels and transported to surface dumps. Filled-stope mining is used now, in order to eliminate the handling of waste, which has

Jan 1, 1938