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By E. Klar, A. B. Michael

Differences in the electrical conductivities of copper powder sintered under reducing, selectively oxidizing, and neutral atmospheres are related to impurities in solution or as precipitated oxides. The precipitation of impurities as oxides during sintering in nitrogen is proposed for maximizing the conductivity of sintered copper. Conductivity equations for two-phase systems are summarized. Selected equations are applied to porous sintered copper and composite structures. A recent review of the influence of impurities on the electrical conductivity of copper by Gregory et al.1 emphasized that an impurity in solid solution has a much more pronounced effect on reducing the electrical conductivity than when present partly or wholly as a second phase. When impurities in solid solution can be precipitated as oxides, the copper is purified with respect to these elements and the conductivity is increased. Cast and wrought copper, therefore, frequently contain an intentional residual oxygen concentration to oxidize and precipitate impurities less noble than copper. Copper powders generally also contain impurities which can contribute to a reduction in the electrical conductivity of the sintered material. The most deleterious impurities commonly found in commercial copper powders which markedly decrease the electrical conductivity when in solid solution but which can be precipitated as oxides include iron, tin, antimony, arsenic, cobalt, and nickel. In addition to impurities, porosity in sintered copper also contributes to a reduction in the electrical conductivity. The work reported herein discusses the influence of impurities, sintering atmospheres, and porosity on the electrical conductivity of sintered copper. These are important factors for controlling the electrical conductivity of materials such as sintered copper electrical contacts. Several publications on the electrical conductivity of sintered copper and composite materials with random pores or obstacles have incorrectly considered the conductivity to be proportional to the volume fraction of conducting material. However, analyses and equations have been proposed, the earliest of which is perhaps Lord Raleigh's of 1892,' which more accurately describe the conductivity of two-phase systems. These equations which in many cases allow one to closely estimate the electrical conductivity of porous sintered materials and two-phase composites will be reviewed and related to the measured electrical conductivity of sintered copper, copper-graphite. and Ag-W composites. INFLUENCE OF IMPURITIES AND OXIDIZING, REDUCING, AND NEUTRAL ATMOSPHERES Zone-Melted and Leveled Copper. The electrical conductivities of an electrolytic copper and a lower-purity compacting grade of copper powder after consecutive treatments in reducing or selectively oxidizing atmospheres are compared in Fig. 1. The powder and drillings from the electrolytic copper ingot were melted and solidified in a graphite crucible under hydrogen. The vertical zone leveling technique of multiple passes in opposite directions was used to obtain a uniform distribution of impurities. The electrical conductivity was measured on machined specimens 3 by 0.10 in. diam of the zone-leveled material and after the same specimens were consecutively treated as follows: 1) heating in hydrogen at 1600°F for 3 hr; 2) heating in air in a sealed tube so that 0.04 pct 0 was introduced; heating was started at 1000°F for 1 hr and continued at 1800°F for 8 hr; the stepwise diffusion treatment was used to avoid loss of copper due to evaporation of copper oxide at higher temperatures; and 3) final heating in hydrogen at 1600°F for 3 hr. A L&N Kelvin Bridge, type 4306, and a test fixture with knife edges 2 in. apart were used to measure the room-temperature conductivity with an estimated accuracy of ±0.5 pct. In all cases the conductivity of the electrolytic copper was approximately 100 pct of IACS. The conductivity of the impure copper was 80 pct of IACS both in the cast state and after heating in hydrogen. However, after the heating in air, the conductivity of the impure material was 100 pct IACS. After again heating in hydrogen, the electrical conductivity decreased to 60 pct of IACS. This decrease is attributed both to the dissolution of impurities and observed intergranular cracks due to the phenomenon of hydrogen embrittle-ment in copper. These data show that the electrical conductivity of commercial copper as represented by a compacting type powder can be increased significantly by the precipitation of impurities as oxides through heat treatment in an oxidizing atmosphere. Sintered Copper Powder. A commercial compacting type of copper powder pressed to various densities was sintered either in nitrogen, dissociated ammonia, or dissociated ammonia followed by a selectively oxidizing atmosphere of air in sealed Vycor tubes so that 0.06 pct O was added to the material. The electrical conductivity was measured perpendicular to the pressing direction on as-sintered specimens of approximately 3 by 0.25 by 0.15 in. The fully dense material was obtained by zone melting and leveling

Jan 1, 1969

By E. Kendall Cork

The traditional financial objective for a single mine company has been to operate as frugally as possible and to pay out most of the earnings as dividends. If the business is cyclical (as it is for most metals) the dividends might fluctuate quite widely. When the mine is exhausted the company disappears. This is still quite a viable strategy for a single mine company. It is not however a viable strategy for the world as a whole. The mining industry is built by mine development companies who can mobilize the people and capital to bring new mines into production. Their skills must include marketing, engineering, finance and other politics. It is very rare for a property to be brought in without the support of a major company that can provide all these services. The exceptions will usually have some other form of big brother support, for example the U.S. government uranium contracts at guaranteed generous prices. The mine development company will seek as a minimum to perpetuate itself by developing new mines in order to replace those which are running out. The more common and more ambitious objective is to grow -- that is to add to its ore reserves and current production by developing more new mines. The financial objectives for that company are very different. Obviously if all the earnings were paid out in dividends there would be nothing left to work with. The first financial policy then is to spend an appropriate amount on exploration for new properties. The next is to retain enough of the earnings to provide the capital for new projects at least sufficient for the equity. There is no magic formula as to what proportion of earnings should properly be distributed as dividends by a growth-oriented mine development company. As a rough rule of thumb distributing half or more will probably leave too little to work on and 30% or so is probably a good balance. However the circumstances differ widely from company to company. It may be useful to set an objective for the rate of growth of a company's earnings. Some have picked rates such as 15% per annum compounded. Others have set a target in real terms which might appear as 10 or 11% plus inflation. Obviously the arithmetic of compound interest is very attractive; however in practice there is much variation. Indeed current returns from existing operations swing widely with the business cycle and there is no assurance that economic new properties will be found according to someone's arbitrary time schedule. For example, Western Mining Corporation Limited in Australia explored for 30 years with little to show for it, but then found the great Australian nickel deposits and more recently the huge Roxby Downs copper. That long dry spell could not have fitted anyone's arbitrary calendar of growth and yet they would not have found such orebodies without that long period of effort. Should they have abandoned the search? Once a new property has been found or acquired there has to be a threshold rate of return on the new capital to be invested against which to evaluate the property's economics. Conventionally this seems to be 15% after tax, a number common in other heavy industries as well. In some cases it is expressed as a lower number plus allowance for inflation. Discounted cash flow analysis is a very useful tool but it does not make the decision. In the end a "go" decision depends on judgment of many factors some of which are numbers used in the DCF calculation whose credibility must be examined. It is curious how frequently investment proposals come in with the rates of return very close to 15%. The project advocates know that a number much less than 15% will not fly and that a number much more is not necessary. With much higher nominal and real interest rates of recent years, even though before tax, logic suggests that the hurdle rate should also rise. The power of compound interest is so great that 20% is very hard to achieve in any cash flow projection but 18% may be a sensible yard - stick. Once again it is remarkable how many project proposals come in with an 18% return. On the record the mining industry as a whole has not been overly restrictive in choosing its hurdle rates of return. This is shown by the abundance of metals in recent years and the failure of metal prices to keep up with inflation. All of the foregoing is standard text book stuff.

Jan 1, 1985

By E. W. Felegy

THE need for improved mine communication to increase efficiency and to insure greater safety has long been recognized. General and unrestricted communication between all points underground, and between the surface and all points underground, is probably the least advanced phase of the mining industry. An ideal system of mine communication must require no fixed wire installations. The equipment must be small, lightweight, and readily portable, and the power requirements low. A system that can be used not only under normal circumstances but also in an emergency, when the continuity of wires, tracks, and pipelines may be disrupted, must function independently of any aid furnished by standard installations. Radio communication offers possibilities of meeting all the requirements necessary for an ideal communication system in underground mines. Transmission of signals must be achieved through one or both of two mediums, through the air in mine openings or through the strata. The results or lack of results obtained by early investigators showed conclusively that radio communication by space transmission cannot be accomplished effectively beyond line-of-sight distances in underground passageways. A radio system underground therefore must depend solely upon transmission through soil and strata. The application of radio to underground mine communication was investigated by many individuals and agencies at different times in the last several decades, but little success was achieved before World war 11.2-0, The results of experiments during the war, and further knowledge gained in experiments with vastly improved communication methods and equipment after the war provided the background for additional research in radio communication in underground mines. During 1950 to 1.952 the University of Minnesota sponsored an investigation to determine the possibility of developing: a system of radio communication universally applicable in underground metal mines in the Lake Superior district. The possibility of using radio equipment to determine the imminence of rock bursts in deep copper mines in that district also was investigated. The investigation supplemented previous and concurrent emergency mine communication studies of the U. S. Bureau of Mines. Testing equipment and laboratory facilities maintained by the Bureau of Mines at Duluth, Minnesota, were used in the research program, which was conducted as a mining engineering graduate research problem by the present writer under the direction of T. L. Joseph and E. P. Pfleider. The radio units used in the research program were designed and built to specification solely to conduct tests of radio communication in mines. Two identical units were used in all tests. Each unit contained a transmitter section, a receiver section, and a power-supply section, mounted on a single chassis. The entire unit was enclosed in a single 10x12x18-in. metal case provided with a leather-strap handle for carrying purposes. The front of the case was hinged to open upward and provide easy access to the single control panel on which all controls were mounted. Storage batteries supplied the operating power for all tests. Standard 6-v automobile batteries were utilized to provide adequate capacity to conduct tests for a full day without exhausting the battery. A frequency range from 30 to 200 kc was covered in eight pre-fixed steps on each unit. The carrier frequencies were crystal-controlled and amplitude-modulated. The receiver employed an essentially standard superheterodyne circuit and was sufficiently sensitive to detect signal strengths of 5 micro v. A heterodyne circuit was employed in the transmitter to obtain the low-carrier frequencies used in the units. Power output of the transmitter, usually less than 2 w, rarely exceeded 3 w in any test. Tests were conducted in mines on the Vermillion iron range in Minnesota, the Gogebic iron range in Wisconsin, the Menominee and Marquette iron ranges in Michigan, and a copper mine in the upper Michigan peninsula. All tests were conducted when the mines were operating normally, and usual mining, maintenance, and transportation activities were in progress, so that any interference caused by normal production activities could be evaluated during the tests. Tests were made between different points underground in each mine, and between underground and surface points at some mines. Test readings obtained at any one mine were calibrated in the laboratory before another series of tests were begun at the next mine. The transmitter and receiver were separated by one or more levels in each test, and generally there was no other means of communication between test points. Two 100-ft lengths of rubber-covered wire were used for antenna wires on each unit in both transmission and reception. The ends of the wires were connected to ground points in one of several methods, depending upon physical conditions at each test site. The wires were clipped to metal rods about 200 ft apart in the back, side, or bottom of the mine opening where the character of the rock permitted driving rods. Both wires were clipped to points about

Jan 1, 1954

By S. R. Bardsley, S. T. Algermissen

Induction, nuclear and sonic well-logging methods were employed in a Green River formation oil-shale analysis and evaluation study conducted in northeastern Uintah County, Utah. The physical and chemical properties of an oil-shale section, previously cored and assayed by conventional methods, were used to evaluate the response of the various logs. The logging program was designed to measure variable properties of oil shale which relate to oil-yield potential in order that a relationship between assay-oil yield and log-determined properties could be identified, thereby permitting a direct determination of yield potential from logs alone. All of the major oil-shale zones and section ttlarkers are recognizable on the logs used in the study. The relationship between the response of the Density and Sonic logs and the assay-oil yield in gallons per ton was suficient to perinit the derivation of equations expressing the relationships. These equations can be used to determine the potential oil yield in gallons per ton of an oil-shale zone or section. The Neutron log response distinguishes the rich oil-shale intervals from the lean intervals, but does not appear to permit establishment of a quantitative relationship. The Garnma-Ray and Induction logs indicate only a qualitative relationship to oil-shale yields. Logging oil shale by Gamma-Gamrna Density and/ or Sonic logging methods will permit a fast, economical and accurate means of evaluating the potential yield of oil-shale deposits. Considerable sums of money have been allocated to Green River formation oil-shale evaluation during the past years by both private enterprise and Federal and state governments. The result of the work accomplished to date is commendable, but the task of fully exploring and evaluating one of the world's greatest reserves of potential energy for economical exploitation is enormous and much information is still needed. Present methods of evaluation consist primarily of sampling and assaying the oil shale for potential yield. The data received are excellent, but are both costly (inasmuch as it requires funds specifically allocated for the evaluation purpose) and time-consuming (as each representative sample must be assayed in the laboratory by specially trained personnel). At the present time, the Green River formation oil-shale province is one of the most active areas in the Rocky Mountain region for exploratory oil and gas drilling. This activity could play a twofold role and serve the function of spear-heading many oil-shale evaluation programs, as it could provide both cutting samples for assaying, geophysical data and modern well logs. This paper deals with a recent study conducted on Green River formation oil shale in which the application of induction, sonic and nuclear well logs to oil-shale evaluation was tested and proved. THEORY AND DEFINITIONS Oil shale may be described as siliceous marlstone, rich in solid organic matter called "kerogen". Kerogen is only slightly soluble in organic solvents, but it will decompose and yield oil vapors and gas when heated to destructive distillation temperatures at about 800 F. The mineral constituents of Green River formation oil shale are found in essentially uniform proportions with one another. The dominant types are, in the general order of abundance, dolomite, calcite, feldspars and quartz. Kerogen is also essentially uniform in its composition, and is about 80 per cent carbon and 10 per cent hydrogen by weight. The ratio of kerogen to the mineral constituents determines the richness or potential yield of the oil shale. This ratio also determines the total physical and chemical properties of the rock and provides a basis by which oil-shale richness may be determined from well logs. Because Green River formation oil shale was deposited in a lacustrine environment, the lithology is laterally consistent over wide areas. The vertical section consists predominantly of thin bands of alternating rich and lean oil shale which have been described by Bradley' as varves. The varves are occasionally broken by thin bands of volcanic ash and tuff and by zones of lean vugular oil shale. The effect that the thin non-oil shale beds and vugular zones would have on the well log analysis was a prime concern in the study. To cope with this possible problem, the logs used in the study were of two types: (1) logs believed to respond favorably to those properties of oil shale which are dependent upon the kero-gen-to-mineral ratio, these logs being the Gamma-Gamma Density log, the Sonic log and the Neutron log; and (2) logs that would respond to litho-logies and properties within the oil-shale section not associated with yield that might result in anomalous responses by the yield-measuring logs. Logs of the second type were the Gamma-Kay log, the Induction log and the Caliper log. THE PRESENT STUDY The present logging study was con-

By Victor deWolfe

INTRODUCTION The Henderson Mine, located near Empire, Colorado, utilizes a continuous panel caving system to extract ore as one of the world's major producers of molybdenum. Any mine using a caving-by-gravity technique of mining must rely on closely controlled draw of the caved ore. This control is essential to insure proper caving action, to avoid damaging load concentrations of weight and to minimize the dilution of ore with waste material. Henderson is no exception. Draw control is a major factor in all production planning, from long- range plans to short-range and day-to-day ore scheduling. Draw control is reviewed constantly and administered daily in an effort to optimize production efficiency, ore recovery, and cave management. MINING METHOD The cave at Henderson is massive, moving slowly through large panels that are 244 m (800 ft.) wide by 610 m (2,000 ft.) long. Generally two cave areas are drawn at one time. The areas under active draw vary in size but can be as large as 244 m (800 ft.) by 244 m (800 ft. ) containing 400 draw points. Each draw point contains 45,360 mt (50,000 st) on the average and takes about two and one half years to exhaust. A complete panel is worked for seven to ten years. No pillar exists between panels, but rather a buffer zone of broken ore, or "static face," is left in each panel to be drawn with the adjacent, yet-to-be-caved panel in efforts of minimizing dilution of a working area from an exhausted one. (Figure 1) Production drifts are driven on 24.4 m (80 ft.) centers through the ore body. Between the production drifts are funnel-shaped draw bells on 12.2 m (40 ft.) x 24.4 m (80 ft.) centers to receive ore from the cave. Each bell is accessed by two draw points, one from the production drift on either side, thus forming a 12.2 m (40 ft.) x 12.2 m (40 ft.) draw pattern. Extraction of the ore is by rubber-tired, 3.8 m3 (5 yd3) load-haul-dump equipment. The LHDs then tram the ore a maximum of 49 m (160 ft.) to ore passes. Cave initiation and bell development are done from the undercut drifts which are parallel to and 17 m (55 ft.) directly above the production drifts. Longhole rings are drilled and blasted from the undercut drifts to define the bells and establish the undercut for caving. (Figure 2) DRAW CONTROL Since the cave line at Henderson is constantly advancing, it is necessary to be continually initiating new cave at one end while exhausting it at the opposite end. There must exist, therefore, an angle on the ore-waste contact in the broken rock from initiation to exhaustion. The basic concept of draw control is to keep this angle as smooth and even as possible, particularly at the time of exhaustion. If this is achieved, draw points are exhausted more or less in a line, avoiding pockets of remaining ore surrounded by exhausted areas. These pockets would cause spotty ore extraction at the time of exhaustion, increasing the amount of dilution occurring while introducing the potential for significant weight problems in the production area. To arrive at the desired angle on the ore- waste contact, maximum tonnage percentages are assigned to each row of draw points increasing at 10% or 15% increments (depending on cave size and velocity of draw) working away from the cave line. The available tonnage indicated by these percentages is the maximum allowable tonnage to be extracted from each draw point until the available tonnage percent- age is increased. As the cave moves, these percentages increase for each draw point regularly. However, in general the tonnage drawn from each draw point is kept at about 50% of this allowable maximum in order to maintain adequate available tonnage in the cave to sustain production for seven months if cave initiation were to cease. This available tonnage cushion is a safeguard built into the draw control program at Henderson to accommodate fluctuations in the rate of cave advance. When draw points move past the row of 100% tonnage availability, they are drawn past the desired 50% at the same increments per row until exhausted. (Figure 3) To achieve proper draw control, the number of LHD buckets to be taken from each draw point is assigned daily. The actual buckets taken, which may at times deviate from the

Jan 1, 1981

By W. A. Schaeffer, M. Albertson

The Yates field is situated in northeastern Pecos County, Texas. Its productive area is about 15,000 acres. Production is chiefly from limestone of Permian age. Depths of wells vary from 1100 to 1800 ft. Initial productions range from a few barrels to 8000 bbl. per hour. The field outlet has always been prorated. Gas-oil ratios originally varied from less than 100 cu. ft. up to 8000 cu. ft. per barrel at allowable production rates. The average ratio was about 500 cu. ft. Fig. 1 shows the structure of the field and the location of the Tippett lease, on which the original experimental tubing work was done. Before the latter part of the year 1929, little actual effort in practice had been given to determination of the conditions under which the highest efficiencies may be realized in naturally flowing wells. For the preceding few years attention had been given to gas-oil ratios and their possible reduction by maintenance of back-pressure by choking at the well head. Some attempts had been made toward reduction of ratio by bottom-hole choking. In late 1929, the Shell Petroleum Corp. started the experimental installation of specially designed flow columns adapted to high-pressure flowing conditions in the Yates field. The objectives in view were the attainment of low gas-oil ratios at low rates of flow and the maintenance of high bottom-hole pressures. All naturally flowing wells should be provided with a suitable eductor string immediately upon completion of the well, so that the benefits of efficient flow will be derived from the beginning. This paper presents a method of tubing for efficient flow and a discussion of some complex factors which influence well behavior. Factors Influencing Gas-oil Ratios Many factors influence the production of gas from naturally flowing wells. The writers believe that in some instances gas control is effected mainly in the reservoir itself, in others in the well bore, and in still others both sets of factors may be significant. Some wells apparently have penetrated productive zones in which practically all of the gas is closely associated with, and mostly dissolved

Jan 1, 1932

By W. L. Fink, M. S. Hunter, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By John Tyssowski

In 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temperatures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several particles had become one unit. From this discovery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the application of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper produced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles. Concurrently, the three metallurgists worked on the problem of effecting a complete union of the cathode particles. Adequate washing was all that was needed to free the particles from electrolyte solution and slimes. A press was designed to produce briquettes of the proper porosity and density, and a method was devised of removing surface oxidation from the particles of cathode, by treatment in an atmosphere of deoxidizing gas at an elevated temperature. The temperature was determined at which the surface cleansing and preheating could be done in one operation, and for this a charging and preheating furnace in which there is maintained a positive pressure of deoxidizing gas atmosphere was designed. And finally, a method of feeding the heated briquettes of deoxidized cathode copper into an extrusion press without contamination from the air was evolved. For the final stage, a press was required because not only heat but pressure was required to obtain complete growth of the new crystals between the cathode particles as well as the elimination of all voids or non-coalesced areas. All essential stages of the process are protected by patents or patent applications in the United States and principal foreign countries, and the copper is produced on a commercial scale.

Jan 1, 1941

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By Louise Barton Freeman, Iley B. Browning, Coleman D. Hunter

During 1942, production of oil in Kentucky reached a total of 4,169,163 bbl. of which 1,807,809 bbl. came from eastern Kentucky. This was more than a million barrels less than in 1941, owing partly to the low price of crude oil, which almost eliminated wildcatting, and partly to spacing regulations, which limited the number of wells drilled in small, shallow pools where the pressures are not sufficient to maintain maximum recovery in widely spaced wells. In eastern Kentucky much of the oil was produced from outliers of the Mauch Chunk series at the disconformable contact of the Mississippian and Pennsylvanian. Although wells producing from this horizon, known as the Maxon, are sprinkled over the entire area, the greatest concentrations are in Martin, Floyd, Knott and Pike Counties. A new 30 to 40-bbl. well has been completed in this formation in ,Pike County, where the carbon ratio is so high that ordinarily oil would not be expected. Pike County is one of the largest producers of Maxon gas, and the offset well to this oil well produced gas. Of the 412 gas wells drilled in Pike County, 12.2 per cent produced gas from the Maxon horizon. During 1942, the old Menifee " Cornif-erous" field, the Mariba-Denniston field, was redrilled between old wells, and although it did not produce any large amount of oil it did contribute 2018 bbl. In the oldest oil field in eastern Kentucky, the Ragland pool, operators are cleaning out abandoned wells and are using this oil for fuel oil. There is a possibility that some of this may be used in the future as distilled fuel oil. Eight wells were completed in 1942 in the Jackson County gas field. The development of Jackson County, which was started in 1934 and in which commercial quantities of gas were encountered at a depth of 1100 to 1200 ft., has become of importance in 1942 with the completion of eight wells, making a total of 24 commercial producing wells with an average rock pressure of 140 lb. At this time the gas is not being marketed. In the last year it has been found that these wells, which produce from the Niagaran dolomite ("Cornif-erous"), respond to acidizing and the production has been thus greatly increased. There has been less development in Estill and Lee Counties than for several years. Two wells were drilled in Greenup County, one of which had a show of oil in the Berea sandstone. One deep test, drilled by the Owens-Libbey-Owens Co. in Lawrence County, was dry. This well was drilled to a depth of 4975 ft. into the top of the Clinton shale sequence. Of the 202 wells completed in Floyd, Martin, Knott and Pike Counties, 187 were gas wells, 3 oil wells and 12 dry holes. In Floyd County 66 per cent of the gas production was from the Devonian-Mis-sissippian black shales, 53 per cent in Martin, 79 per cent in Knott and 65 per cent in Pike. This is probably the largest continuous gas field east of the Mississippi

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By C. W. Phillips, R. S. Busk

With most cast metals the grain size may vary within wide limits, depending upon the conditions at the moment of freezing. These conditions are subject to control in magnesium-base alloys, by proper melting and superheating techniques, enabling production of quite uniform and fine-grained castings, almost independent of section thickness. However, such variations of grain size as do exist, in common with all metals, are reflected in corresponding changes in mechanical properties. It is the intent of this paper to present data giving the relationship between grain size and mechanical properties. Data are also included on the combined effects of grain size and micro-porosity. In addition, a short discussion of factors influencing the grain size of sand castings is included. Measurement OF Grain Size By grain size is meant the statistical distribution of volumes occupied by the individual crystallites in a metal section. Since this is almost always impossible of direct measurement, several methods of estimating and expressing the size have been evolved. Most exact methods make use of the microscope. This involves study of a single plane cut at random through the metal. What is seen in the microscopc are polygons, each the cross section of a grain. The diameters or areas of these polygons are then measured and the grain size is expressed as an average diameter, number of grains per unit area, average area per grain, or, rarely, average volume per grain. Rutherford, Abom, and Bain3 have discussed extensively the errors involved when using a plane section to estimate volume. They clearly point out that the tendency is to underestimate the true grain size because of the nature of the measurcment. The A.S.T.M. recommends that measurement be made by comparison with a standard chart, by means of Jeffries' planimetric method4 or Heyn's intercept method. The Society recommends that the notation be in terms of the number of grains per unit area (as is the grain-size number used for steel) or as an average diameter, expressed in inches or millimeters (as for copper and brass). The method of measurement used for this study was comparison with a standard chart, which has been described by P. F. George.5 The chart was constructed by photographing at Ioo diameters a uniform specimen with an average grain diameter of 0.003 in. The average diameter of this specimen was determined by numerous measurements, using both the Jeffries and Heyn methods. The other grain sizes were then obtained by appropriate enlargemcnt of the master sample. Careful comparison of the chart method with other methods on identical samples indicates that though the differences be-

Jan 1, 1945

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By G. I. Madden, L. H. Van Vlack

WhEN basic refractories which contain peri-clase, MgO, are used in steel furnaces, they are altered by iron oxide to form magnesiowiistite, (Mg,Fe)O, and an iron-rich magnesioferrite, (Mg,Fe)Fe2O4. Silica, which is usually present, produces a silicate liquid that surrounds the solid phases. The individual crystalline grains of the above two solid phases grow at elevated temperatures. Previous papersL" showed that, if either periclase or magnesiowiistite is present as the only solid phase, its grain size increases in proportion to temperature and in proportion to the square root of time; the growth rate is reduced slightly if the amount of silicate liquid is increased. Similar results have been observed for iron-rich magnesioferrite.3 To determine the effect of the presence of two solid phases on the rate of grain growth, micro-structural studies have been made on samples containing both magnesiowustite and magnesioferrite. The experimental procedure was the same as that followed in the previous studies of this type.'12 Briefly, this included determination of compositions from the available phase relationships4 that would produce the two phases of interest at the firing temperature and using reagent-grade raw materials to prepare mixtures of these compositions. The mixtures were pressed into pellet-size samples and then fired at the desired time and temperature. The samples were water-quenched to preserve the microstructure present at the firing temperature. Standard reflected-light metallographic techniques were used for sample examination and sample analysis. Grain sizes were determined by measuring the mean diameter of a number of randomly selected grains in a two-dimensional microsection. A large cross section of the sample was covered to prevent biased data resulting from such effects as localized differences in the radius of curvature of the crystal grains. Examination indicates that grain growth is restricted when more than one solid phase is present. This is illustrated in Fig. 1 for: (a) magnesiowustite plus a silicate liquid; (b) magnesioferrite plus a silicate liquid; and (c) magnesiowiistite and magnesioferrite plus a silicate liquid. Fig. 2 plots the

Jan 1, 1964

By William C. Marshall, Frank G. Norris

THE term "total operation" is meant to include problems that cannot be answered from the standpoint of either the blast furnace or the open hearth separately but must be studied by considering the interrelations of these two processes. There are other ways of expressing this idea, such as reference to the blast furnace and the open hearth as an integrated process or by emphasizing the interrelation and interaction of the two processes. Much progress has been made in metallurgy and other fields by breaking complicated processes and reactions into simpler parts and studying each of these intensively. This intensive study frequently is done under the controlled conditions of the laboratory experiment. The entire process is understood better by this specialized study of each of its parts. This procedure is so satisfactory that an understanding of unit operations is a fundamental requirement of chemical engineering. Much discussion of the open-hearth process is in terms of one heat or one furnace. By this is meant that the conclusions apply to one furnace, wherever it may be. Furnaces seldom occur singly; they are located in groups and these groups are located in steel plants having characteristic blast-furnace equipment. Problems that are affected by the number of furnaces operating, by the number of blast furnaces in the plant and by the fact that the open hearth shop is dependent on the blast-furnace capacity rather than on its own needs for the amount of iron available are among those which, in contrast to "unit operations," we have chosen to call "total operations," Many of these problems, such as charging delays and the general mechanical problem of material handling, are so familiar that merely to define "total operations" brings them to mind. These problems are of such importance that already they have received careful thought and study and probably will merit further study. As will be shown later, these mechanical problems are so intimately related to metallurgical problems of total operations that the effect of certain changes cannot be ascribed with certainty to either a mechanical or a metallurgical cause entirely. Although the problems coming under the general term of "railroading" are included in the problems of total operations, two others are selected for the discussion of this paper. One of these is strictly a problem of composition; the other is strictly a problem of tonnage production. The problem of phosphorus is present whenever basic open-hearth slag is used in the blast-furnace burden. This practice has not secured universal acceptance chiefly because of difference in preference for high-manganese or low-manganese pig iron. If high-manganese (2.00 per cent) iron is to be made, open-hearth slag as a source of manganese is usually cheaper than man

Jan 1, 1943

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By John Tyssowski

In 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temperatures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several particles had become one unit. From this discovery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the application of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper produced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles. Concurrently, the three metallurgists worked on the problem of effecting a complete union of the cathode particles. Adequate washing was all that was needed to free the particles from electrolyte solution and slimes. A press was designed to produce briquettes of the proper porosity and density, and a method was devised of removing surface oxidation from the particles of cathode, by treatment in an atmosphere of deoxidizing gas at an elevated temperature. The temperature was determined at which the surface cleansing and preheating could be done in one operation, and for this a charging and preheating furnace in which there is maintained a positive pressure of deoxidizing gas atmosphere was designed. And finally, a method of feeding the heated briquettes of deoxidized cathode copper into an extrusion press without contamination from the air was evolved. For the final stage, a press was required because not only heat but pressure was required to obtain complete growth of the new crystals between the cathode particles as well as the elimination of all voids or non-coalesced areas. All essential stages of the process are protected by patents or patent applications in the United States and principal foreign countries, and the copper is produced on a commercial scale.

Jan 1, 1941

By Arnlf Muan, Bert Phillips

The quenching technique has been used for- a study of phase velntiorzs within the composition triangle 2CaO.Fe2O3-FeO.Fe2O3 Fe2O3 of the system Ca-Fe-O. Desired total compositions of sanzples were attained by weighing of starting materials in required proportions and keeping them in sealed 80 pct Pt 20 pct Rh tubes during equilibration .runs. The liquidus surface has been delineated. the existence of two ternary compounds has been established, and seven ternary inwariant situations have been determined. ONE unit within the research program on refractory oxides in progress in our laboratories is the study of phase relations in the system Ca-Fe-Si-O. The present paper deals with the ternary system 2CaOFe2O3-FeO.Fe2O3-Fe2O3, which is only a small part of the enormously complex quaternary system. Many of the phases occurring in iron ore sinter products have compositions which can be closely approximated within this ternary system, and a knowledge of stability relations existing among these phases may be expected to be a useful guide for improving sintering operations. Two fundamentally different experimental approach es are commonly used in studies of systems containing iron oxides, both permitting control of the oxidation state of Fe. One method consists in keeping constant the oxygen partial pressure of the gas phase in equilibrium with condensed phases (liquid and crystalline). In the other method, which is the one used in the present investigation, the total composition of condensed phases is kept essentially constant by keeping the samples in a gas-tight container. The details of this experimental procedure will be described in a later section. PREVIOUS WORK Extensive studies of phase relations in the bounding binary system FeOFe2O3-Fe2O3 have been reported by Greig, Posnjak, Merwin, and Sosman,' by Darken and Gurry,2, 3 and recently by Phillips and Muan.4 A diagram summarizing the results of these studies is shown in Fig. 1. Particular attention is

Jan 1, 1961

By M. S. Hunter, W. L. Fink, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By Iley B. Browning, Louise Barton Freeman, Coleman D. Hunter

During 1942, production of oil in Kentucky reached a total of 4,169,163 bbl. of which 1,807,809 bbl. came from eastern Kentucky. This was more than a million barrels less than in 1941, owing partly to the low price of crude oil, which almost eliminated wildcatting, and partly to spacing regulations, which limited the number of wells drilled in small, shallow pools where the pressures are not sufficient to maintain maximum recovery in widely spaced wells. In eastern Kentucky much of the oil was produced from outliers of the Mauch Chunk series at the disconformable contact of the Mississippian and Pennsylvanian. Although wells producing from this horizon, known as the Maxon, are sprinkled over the entire area, the greatest concentrations are in Martin, Floyd, Knott and Pike Counties. A new 30 to 40-bbl. well has been completed in this formation in ,Pike County, where the carbon ratio is so high that ordinarily oil would not be expected. Pike County is one of the largest producers of Maxon gas, and the offset well to this oil well produced gas. Of the 412 gas wells drilled in Pike County, 12.2 per cent produced gas from the Maxon horizon. During 1942, the old Menifee " Cornif-erous" field, the Mariba-Denniston field, was redrilled between old wells, and although it did not produce any large amount of oil it did contribute 2018 bbl. In the oldest oil field in eastern Kentucky, the Ragland pool, operators are cleaning out abandoned wells and are using this oil for fuel oil. There is a possibility that some of this may be used in the future as distilled fuel oil. Eight wells were completed in 1942 in the Jackson County gas field. The development of Jackson County, which was started in 1934 and in which commercial quantities of gas were encountered at a depth of 1100 to 1200 ft., has become of importance in 1942 with the completion of eight wells, making a total of 24 commercial producing wells with an average rock pressure of 140 lb. At this time the gas is not being marketed. In the last year it has been found that these wells, which produce from the Niagaran dolomite ("Cornif-erous"), respond to acidizing and the production has been thus greatly increased. There has been less development in Estill and Lee Counties than for several years. Two wells were drilled in Greenup County, one of which had a show of oil in the Berea sandstone. One deep test, drilled by the Owens-Libbey-Owens Co. in Lawrence County, was dry. This well was drilled to a depth of 4975 ft. into the top of the Clinton shale sequence. Of the 202 wells completed in Floyd, Martin, Knott and Pike Counties, 187 were gas wells, 3 oil wells and 12 dry holes. In Floyd County 66 per cent of the gas production was from the Devonian-Mis-sissippian black shales, 53 per cent in Martin, 79 per cent in Knott and 65 per cent in Pike. This is probably the largest continuous gas field east of the Mississippi

Jan 1, 1943