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By Samuel B. Christy

" The man is always greater than his work." The training of the men who are to develop the mineral resources of the world is the most important problem connected with mining engineering. It becomes ever more important to civilization as the mineral wealth of the earth approaches exhaustion. I have therefore decided to consider a few of the more important problems arising in the training of the mining engineer, and especially those arising in America. , The Peculiar Nature of Mineral Wealth. Mining and Agriculture are the two fundamental arts. Without the latter our existence would be precarious; without the former, our civilization impossible. Agriculture furnishes that regular supply of food and raiment which leads to the growth of large communities in which cultivated leisure first becomes possible; while mining furnishes the metallic thread from which is woven that complex fabric we call civilization. But in these two arts the conditions for success are widely different. Most of the crops that the farmer reaps may be harvested year after year, and the proper fertilizers being added, he may continue the annual harvest indefinitely, while, as a result of cultivation, his farm becomes yearly more valuable. But the crop the miner reaps can be harvested but once in the history of the race. Our mineral wealth has taken unknown ages to mature in the bosom of the earth. The ripened fruit can be plucked but once. There are no fertilizers for worked-out mines. It never pays to work over a mine that has been

Jan 1, 1906

By Gordon M. Yocom

A PROPER consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer's experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modern methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that

Jan 1, 1941

By Robert Henderson

SEVERAL very interesting articles have been written on the caving system of mining, but most of these papers have dealt separately with the slusher system or the chute and grizzly system. In this paper, a comparison will be made of the two methods, both of which are being used at the Climax mine. The mine is on the Continental Divide, in central Colorado, at an altitude of approximately 11,500 ft. above sea level. The long, cold winters, characteristic of the high Rockies, create a number of operating problems not usually found in other mining areas. THE ORE BODY The Climax ore body is just east of the Mosquito fault. This structural deformation has brought the granite on the east against the sedimentary rocks on the west. The ore occurs in an intensely altered granite and schist around a silicified granite core. The ore is in a highly fractured zone of moderate silicification. The principal mineral, molybdenite, is found in these fractures. Barren dikes of granite porphyry cut through the ore body and core with no apparent regularity. The grade of the ore is fairly uniform and gradually decreases toward the footwall core and also into the hanging-wall granite. The footwall and hanging wall are determined entirely by assays. The ore body is roughly dome-shaped, with the apex truncated at the surface. It is covered to varying depths with talus. A horizontal section of the ore body on the Phillipson level appears as an annular ellipse surrounding the footwall core. The ring of ore varies in width from 300 ft. to as much as 800 ft. The north-south axis of the core is about 1200 ft. and the east-west axis is about 1800 ft. In the ore zone, the rock is sufficiently strong to maintain reasonably large openings, and openings larger than haulage drifts usually have to be supported. The ore is cut by a great many fractures and shears and breaks into rather large blocks when caved, necessitating considerable secondary blasting. The waste that overlies the ore body breaks relatively fine in comparison with the size of the blocks of the caved ore and tends to run through the broken ore in the cave, causing dilution unless the draw is carefully controlled. MINING SYSTEMS For several years the ore was mined by the chute and grizzly system, a system that differs from that used in other caving mines only in the size of openings and equipment. In the chute and grizzly system, main haulage laterals were driven along the footwall core and also along the

Jan 1, 1944

By K. E. Brown, F. W. Jessen

By utilizing an 8,000-ft experimental field well equipped with 10 gas-lift valves and 10 Maihak pressure recorders, gas-lift tests were conducted with port sizes ranging from 5/16 through I in. The well was equipped to provide accurate means of measuring surface pressures, temperatures, quantity of injection gas and fluid production. The tests were conducted in 2%-in. OD tubing, and the well was making 95 per cent water. A complete evaluation of gas-lift-valve port sizes shows the relationship of per cent recovery, gas-liquid ratios, minimum pressure created at the operating valve and horsepower requirements for each port. The length of time necessary for the fluid in the tubing to reach equilib.rium conditions after each cycle was recorded. Fallback of fluid at depths of 477, 969, 1,685, 2,493 and 4,290 ft was noted. For each port size, pressure loads of 2.50, 300, 350, 400 and 450 psi were lifted with a valve operating at approximately 550 psi at 6,000 ft. Gas-liquid ratios for each load were varied from excess gas to a gas volume per cycle whereby the load failed to reach the surface. Numerous curves are presented in evaluating the accumulated dara. The results show a 1-in. port to be the most efficient under all conditions. The production of intermittent liquid slugs against different-sized surface chokes was evaluated. These tests were conducted from a 7/16-in. ported valve at 4,072 ft. Tests indicate that, when possible, a %-in. in diameter choke or larger should be used at the surface. In the past few years most of the advancement in gas-lift operations has been made in continuous-flow operations. Yet, it is estimated that at least 70 per cent of the wells on gas lift in the United States are of the intermittent type. Since the term "slug flow" is sometimes used in both intermittent- and continuous-flow operations, it would be well to distinguish between the two types of flow. Continuous-flow gas lift is defined as a method whereby the fluids are produced at a continuous rate at the surface. This generally requires a continuous injection of gas through a surface choke; however, various other control devices sometimes are installed to eliminate freezing, to shut-off gas during natural flow periods, etc. The actual flow of fluids in the tubing may be of the slug type (one of many flow patterns known to exist in continuous flow). Intermittent flow is defined as a method of gas lift whereby the liquid is produced in separate piston-type slugs. Perhaps this type of flow could best be thought of as a ballistic-type flow where the liquid leaves bottom as a piston, propelled by a slug of expanding gas. Gas generally is injected through some type of control at the surface at predetermined intervals. However, the valve may have characteristics whereby gas can be injected through a small choke and still result in a ballistic-type flow. The purpose of the experimental work was to evaluate the most efficient port size to be used on the operating valve for the ballistic type of lift and, in addition, to establish the importance of utilizing a surface choke large enough to allow slugs to be produced without detrimental effects. This work is part of a compre- hensive study of both intermittent-and continuous-flow gas lift, representing a joint project conducted by the Ohio Oil Co., the Sun Oil Co., Otis Engineering Corp, and The U. of Texas. The problem of evaluating port sizes has been given little previous attention. Some work undoubtedly has been done which has not been published to date. Some tests were conducted when the wireline, mechanically-opened valve (Nixon) first came on the market. This valve was capable of utilizing full tubing area as its port size. It is known that this was a very efficient valve, but to the authors' knowledge the results of tests have never been published. EXPERIMENTAL EQUIPMENT These tests were conducted on an actual field well, the Ohio-Sun Unit Well No. 2-E, in the North Markham-North Bay City field, Matagorda County, Tex. The well incorporated 23/8-in. OD tubing and produced 95 per cent water. Since the running of equipment was to be quite elaborate and expensive, a well was selected in which both intermittent- and continuous-flow tests could be conducted. This particular well was capable of producing in excess of 1,000 B/D of liquid (95 per cent salt water), yet with a 3/64-in. in diameter bottom-hole choke, production was controlled to 82 B/D. Most of the intermittent tests were conducted at this low rate. Figs. 1 and 2 show all the surface and down-hole equipment. As can be seen, every attempt was made to insure that ample equipment was available for reliable testing procedures. Fig. 1 shows the surface testing equipment. The input gas was controlled first by a regulator, then

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By B. H. Sage, R. T. Carter, W. N. Lacey

The phase behavior of a number of binary systems consisting of parafin hydro-carbons has been determined in recent years. In addition, the composition of the coexisting phases of mixtures of crude oil and natural gas has been investigated.~ However, the latter study did not include information concerning the influence of the concentration of a component upon its distribution between two coexisting phases. Owing to the paucity of such information it was considered desirable to investigate in some detail the composition of the coexisting phases in the methane-propane-n-pentane system throughout the greater part of the two-phase region at a tempera-ture of 100°F. Information of this nature also permits the establishment of the critical behavior of this ternary system. Method The compositions of the coexisting phases in this ternary system at 100°F. were deter-mined by withdrawing samples from a pres-sure vessel containing a heterogeneous mixture of the three components that had been brought 10 equilibrium by mechanical agitation at the desired pressure and tem-perature. The samples were withdrawn under such conditions that the equilibrium was not disturbed and the composition of each of the phases was ascertained by means of the conventional low-temperature fractionation procedure. The apparatus employed in this investi-gation was nearly the same as that utilized in an earlier study of the methane-pentane system.~ Several minor modifica-tions in the arrangement of the apparatus were made in the interest of simplifying the procedure and avoiding the possibility of condensation in the tubing connecting the equilibrium apparatus with the analyti-cal equipment. The pressures were meas-ured by means of a pressure balance with a precision of 0.5 lb. per sq. in. It is believed that the equilibrium pressure was ascer-tained with an uncertainty of not more than 2 lb. per sq. in., even though small varia-tions in pressure obtained during the withdrawal of the samples. The tempera-ture of the equilibrium equipment was maintained by use of an automatically controlled oil bath. The bath temperature was determined by means of a copper-constantan thermocouple, the electromo-tive force being determined by means of a potentiometric circuit of such a nature as to reduce the uncertainty of the tempera ture to less than O.I f. The fractionating column employed in the determination of the composition of the gas phase had a diameter of 0.12 in. and was approximately 4 ft. long, while the column employed in the analysis of the liquid phase was 0.18 in. in diameter and about 5 ft. long. Each column was equipped with the conventional constant-volume receivers, which were maintained at a constant temperature by means of an automatically controlled oil bath. In nearly every case the distillation in thr neighborhood of the transition between

Jan 1, 1941

By W. N. Lacey, R. T. Carter, B. H. Sage

The phase behavior of a number of binary systems consisting of parafin hydro-carbons has been determined in recent years. In addition, the composition of the coexisting phases of mixtures of crude oil and natural gas has been investigated.~ However, the latter study did not include information concerning the influence of the concentration of a component upon its distribution between two coexisting phases. Owing to the paucity of such information it was considered desirable to investigate in some detail the composition of the coexisting phases in the methane-propane-n-pentane system throughout the greater part of the two-phase region at a tempera-ture of 100°F. Information of this nature also permits the establishment of the critical behavior of this ternary system. Method The compositions of the coexisting phases in this ternary system at 100°F. were deter-mined by withdrawing samples from a pres-sure vessel containing a heterogeneous mixture of the three components that had been brought 10 equilibrium by mechanical agitation at the desired pressure and tem-perature. The samples were withdrawn under such conditions that the equilibrium was not disturbed and the composition of each of the phases was ascertained by means of the conventional low-temperature fractionation procedure. The apparatus employed in this investi-gation was nearly the same as that utilized in an earlier study of the methane-pentane system.~ Several minor modifica-tions in the arrangement of the apparatus were made in the interest of simplifying the procedure and avoiding the possibility of condensation in the tubing connecting the equilibrium apparatus with the analyti-cal equipment. The pressures were meas-ured by means of a pressure balance with a precision of 0.5 lb. per sq. in. It is believed that the equilibrium pressure was ascer-tained with an uncertainty of not more than 2 lb. per sq. in., even though small varia-tions in pressure obtained during the withdrawal of the samples. The tempera-ture of the equilibrium equipment was maintained by use of an automatically controlled oil bath. The bath temperature was determined by means of a copper-constantan thermocouple, the electromo-tive force being determined by means of a potentiometric circuit of such a nature as to reduce the uncertainty of the tempera ture to less than O.I f. The fractionating column employed in the determination of the composition of the gas phase had a diameter of 0.12 in. and was approximately 4 ft. long, while the column employed in the analysis of the liquid phase was 0.18 in. in diameter and about 5 ft. long. Each column was equipped with the conventional constant-volume receivers, which were maintained at a constant temperature by means of an automatically controlled oil bath. In nearly every case the distillation in thr neighborhood of the transition between

Jan 1, 1941

In Bulletin J 1, recently published by the Traylor Engineering and Manufacturing Co., it is stated that the largest jaw crusher ever built has a jaw opening of 66 in. by 86 in. and weighs 680,000 1b. It is said to be in successful operation and has a capacity of 490 tons per hour crushed to 12-in. size; 415 tons per hour crushed to 10-in. size; 330 tons per hour crushed to 8-in. size. The same company, in its Bulletin G 3, gives a diagram showing the percentage of a crushed product which will pass through screens of different sizes of perforation from a machine adjusted to a certain size screen. This diagram is reprinted below for the information of our members and the following notes apply to it. In order to prevent an excessive amount of fines, crushing machines are usually set so that 15 per cent. of the product will be larger than the maximum size desired, and this oversize is then recrushed by smaller

Jan 10, 1916

By George M. Fowler, Joseph P. Lyden

PaGE Scope of this Report.................................................... 206 Production of Tri-State District.......................................... 207 Historical Sketch....................................................... 207 Location and Topography............................................... 211 Geology............................................................... 212 The Tri-State District.............................................. 214 Stratigraphy........................................................... 217 General Geological Section in Tri-State Region....................... 217 Stratigraphic Section of Mineralized part of Boone Formation........... 218 Stratigraphic Section Bird Dog Well.................................. 219 Metamorphism........................................................ 220 Structure............................................................. 225 Regional.......................................................... 225 Due to Metamorphism.............................................. 229 Ore Deposits.......................................................... 231 Types............................................................ 232 Hard-ground Deposits.......................................... 232 Brecciated................................................. 232 Stratified............................................ 232 Sheet Ground............................................. 232 In Dolomite............................................... 233 In Shale.................................................. 233 Soft-ground Deposits.......................................... 233 In the District as a Whole....................................... 233 Ore Minerah and Analysis......................................... 233 Paragenesis....................................................... 234 Conclusions........................................................... 236 Structure.......................................................... 236 Genesis of the Ore.................................................. 237 Future of the District............................................... 239 Acknowledgments..................................................... 239 Discussion............................................................ 239 Scope of This Report The Tri-State district. as outlined in this paper. refers to the entire mineralized area in sout'hwestern Missouri. southeastern Kansas and

Jan 1, 1932

By L. C. Graton

I. INTRODUCTION. The Relations of Scale in Geologic Work. MANY features of human accomplishment rest upon the possibility of representing natural objects on a scale of different magnitude from the actual one. Most drawings, for example, are of very different scale from that of the object depicted, and indeed are useful mainly on this account. More important than the question of mere convenience, however, is that of meeting the physical limitations of vision.1 Thus, a mural

Jan 5, 1913

By F. O. Willhofft

The symposium on mine safety held in connection with the annual meeting of the Institute three years ago, it. was pointed out that "at present no convenient, reliable, accurate means for determining the gas content of mine air is available, for use by the ordinary mine man." In a letter addressed to Coal Age and published on Feb. 25, 1925, Thomas T. Read, then Director of the Safety Service of the Bureau of Mines, stated: "It is to be hoped that sometime in the near future some-one will invent a reliable methane indicator that is con-venient to, use and will permit the keeping of all flames of every character out of bituminous mines, through doing away with the safety lamp." The Martienssen methane detector, which has re-cently received the official approval of the Bureau of Mines, is intended to. meet the demand for such an in-strument as expressed at that meeting and on many other occasions. The characteristics which qualify it for the task are the following: (1) simplicity; (2) small bulk and light weight; (3) ruggedness; (4) accuracy sufficient for the requirements; (5) safety; and (6) dependability. The principle on which the working of the instrument is based may best be explained by giving a brief out-line of the various stages of development through which the inventor, Professor Martienssen of the University of Kiel, Germany, advanced to the final solution of the problem which he had undertaken to solve.

Jan 2, 1928

By W. T. Cardwell, R. L. Parsons

This paper discusses the practical problem of estimating a single equivalent permeability for an oil reservoir, or a portion thereof, whose actual permeability varies in an irregular manner. Limiting averages for general types of permeability variation are developed, and illustrated by examples involving important, specific types of variation. Introduction The theory of the flow of fluids through porous media1"4 is becoming increasingly important in predictions of oil-reservoir behavior. In practical applications, however, reservoirs are seldom found to which simple theory strictly applies. Actual reservoirs have complicated shapes and nonuniform permeabilities and porosities. This paper discusses the problem of estimating a single equivalent permeability for an oil reservoir, or a segment of an oil reservoir, whose actual permeability varies in an irregular manner. The equivalent permeability of a reservoir segment is defined as the permeability of a homogeneous segment of the same dimensions that would pass the same flux under the same pressure drop- It is the permeability value that can be used in simple theoretical formulas to calculate the reservoir behavior. To the authors' knowledge, previous theoretical calculationst on systems of nonuniform permeability have been carried out only by Muskat'"; and he has not dealt with irregular variations, except in writing down the general differential equation for the pressure in variably permeable systems.lb In practical work, many calculations necessarily have been made to estimate equivalent permeabilities from the permeabiiity profiles obtained by core analyses. Regarding such calculations, Johnston and Sherborne6 say: Simple arithmetic and weighted averages have been tried on many wells and it has been found that, where frequent sampling has occurred, the arithmetic average is as satis- factory as a weighted average. It is possible that the application of statistical methods to the analysis of permeability data as recently presented by Law8 may prove fruitful. L,, has made a valuable contribution in showing how statistical analyses may aid in picturing the characteristics of a reservoir from those of a necessarily limited number of core samples. It is believed however that the particular problem of the estimation of equivalent permeabilities can be most directly approached from a fluid dynamical viewpoint as given in the present paper. An example is presented of the use of the conclusions herein in conjunction with Law's method. Theory In order to approach the problem of heterogeneity simply, it is interesting to consider a square block composed of four smaller, homogeneous, square blocks of porous medium, two of which have a

Jan 1, 1945

By R. B. Falk, F. E. Luborsky

Small iron particles in mercury pow by diffusion of iron atoms through the mercury. Iron particles, with diameters about 200Å, have been stopped from gvowing in size, even up to the boiling point of mercury, by the addition of a third metal. The metal additives were classified according to whether they produced 1) negligible inhibition, 2) some inhibition, or 3) marked inhibition of the growth rate. Metal additives which resulted in a marked inhibition of iron-particle growth form a stable monolayer on the iron particles. Only those metals which may form compounds with iron showed this pronounced effect. The one exception was manganese. Metal additives which resulted in no inhibition of growth, showed no evidence for adsorption and could not form compounds with iron. None of the added metals, even those which strongly inhibited particle gvowth and thus had adsorbed on the particle surface, actually formed any compounds with iron at room temperature at the concentrations required for complete inhibition of growth. ThE stabilization of the size and shape of metallic particles dispersed in liquid metals has important technological implications in "homogeneous" nuclear reactor systems and in elongated particle magnets and is directly related to the problem of corrosion by liquid metals. Growth in these par-ticulate systems may occur by diffusion of atoms from surfaces of high energy, corresponding to a small radius of curvature, to surfaces of low energy or large radius of curvature. Thus, small particles dissolve and large particles grow to increase the average diameter of the particles. reenwood' has analyzed this diffusional growth of a system of particles containing a distribution of sizes and has obtained reasonable agreement with data on the growth of uranium particles in liquid sodium and UPb3 particles in liquid lead. Greenwood concluded from his analysis that the chief factors promoting stability of dispersed particles growing by a diffusion mechanism are large mean radius, high density, and low molecular weight with low values of the solute diffusion coefficient, the solubility, and the interfacial tension. In the case of elongated particle magnets the system of interest is that of iron particles dis- persed in mercury. Previous work,2 concerned with "spherical" particles in mercury, has indicated a diffusional growth mechanism similar to that discussed by Greenwood. It has also been shown3'4 that the addition of certain metals to Fe-Hg dispersions results in the formation of a monatomic layer of adsorbed atoms on the iron particles. In this paper we will show that this adsorbed layer provides the decrease in the iron-atom flux through the mercury necessary for size stabilization. The general features of the stabilization of the iron particles in mercury through the formation of this "coating", with many different metals, will be described. EXPERIMENTAL RESULTS Iron particles in mercury were prepared by elec-trodeposition,2, 4 and measurements2, 4 of coercive force HCi) and saturation induction (Is) were used to follow changes in size and composition during thermal aging in the mercury in the presence of relatively small amounts of an added metal. In Fig. 1 is plotted the aging behavior of spherical particle samples in the presence of some of the added metals to be discussed. The iron particles have an initial average diameter of 180Å. Each sample was aged for 20 min at each temperature in succession in the presence of a twofold to threefold excess of added metal over that required to form a monolayer on the iron particles. These are the same samples used previously3 to study the adsorp-

Jan 1, 1965

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By L. H. Robinson

A proposed method of drilling utilizes sequential detonation of two types of explosive charges delivered to the hole by a conventional drilling fluid through pipe. A shaped charge first produces a long thin hole. A second charge, called a gauging charge, is pumped into the thin hole, explodes, and enlarges it to full gauge. In one suggested configuration, the explosives are contained in cylindrical capsules 4- to 5-ft long. A drilling head is positioned 2- to 3-ft off bottom. When a capsule is pumped to the bottom of the hole and stops, pressure inside the drill pipe increases and differential pressure detonates the explosive. Primacord along the length of the capsule disintegrates the capsule. The debris circulates out of the hole with the drilling fluid. The gauging-charge action was examined using 2-ft cubes of Berea sandstone. The sandstone (18 per cent porosity) was vacuum-saturated with water and surrounded by concrete. To prevent reflected tensile pulses, the acoustical impedance of the concrete matched that of the sandstone. A 750-psig pressure was applied to a drilling fluid within a shaped-charge-formed hole before detonating the gauging charge. In these tests, 190 gm of rock were removed for each gram of explosive detonated. A similar series of experiments on low-porosity (0.40 per cent) metamorphic limestone provided a more rigorous test. Extensive fracturing from the gauging-charge action prevented an estimate of the volume of the expanded hole. The diameter of the hole was irregular, ranging from about 2 to 4 in, or about fivefold larger than the hole created by the shaped charge. INTRODUCTION In the past, explosives have found a varied but somewhat limited use in the oil field. An early well stimulation technique, still in use today, in vo lves shooting ni troglycerin to en large the borehole and to increase matrix permeability near the wellbore. Bullets and jets are now the conventional method of perforating casing and tubing. Detonations are frequently used to "back off" or "shoot off" stuck pipe and, of course, seismo-graphic work has long depended on explosive-generated pulses to find attractive earth structures. Efforts to use explosives in drilling operations have received limited examinations1-3 which, in one respect, is surprising because explosives offer one way to transmit large amounts of energy directly to the bottom of the hole. Recently, Ostrovskii l described a Russian method of drilling with explosives that utilizes small capsules containing explosives which are pumped into the mud stream to the bottom of a borehole. As the capsules leave the end of the drill pipe, a detonation mechanism is armed. Impact detonates the explosive. In another configuration, two liquids (an oxidizing agent and fuel) in the capsule are separated by a frangible membrane. Separately, the liquids are nonexplosive. Near the bottom of the drill pipe, the capsule passes through a narrow constriction which ruptures the membrane. The mixing of the liquids produces an explosive. Impact is again used to detonate the explosive. About the time Ostrovskii was developing his method, Humble Oil & Refining Co. was independently doing research on another explosive drilling concept based on the sequential detonation of two types -of explosive charges. The proposed technique consisted of alternately pumping a shaped charge and then a "gauging charge" down a well. The shaped charge should drill a long, tapered hole, and the gauging charge should expand it to full gauge. This paper presents the visualized drilling concept and gives results of laboratory work which showed that sequential firing of charges can form hole at an attractive charge-to-rock removal ratio. An important finding was that increased environmental pressure, which is to be expected in wells, increases rock removal efficiency of the gauging charge.

Jan 1, 1966

By J. A. Snyder, W. L. Finlay

SEVERAL notable studies of the effects of sub- stitutional solutes have been reported. Outstanding among these for its elucidation of general principles, is the summarized work of Hume-Rothery and coworkers.1 For a systematic study of the effects of substitutional solutes on the mechanical properties of the solvent lattice, the work of Brick, Martin, and Angier² on copper; of Frye and coworkers³,4,5 on copper and silver; and of Lacy and Gensamer6 and of Austin7 on iron may be mentioned. Titanium is one of the few elements offering the possibility of a similar study of interstitial solutes since, unlike most metallic elements, it exhibits extended solid solubility for most of the interstitial solutes—hydrogen, boron, nitrogen, oxygen, and carbon. This paper reports a survey of the effects of dilute solutions of nitrogen, oxygen, and carbon on the mechanical properties of high-purity alpha titanium. Previous Work: Van Arkel and De Boer showed" that high purity titanium was quite ductile and De Boer, Burgers and Fast established".' that not only were oxygen and nitrogen very soluble in solid titanium but that, long before the limit of solid solubility of either had been reached, these interstitial solutes rendered the metal brittle. Their electrical resistance data as a function of

Jan 1, 1951

By Chas. B. Dudley

A Discussion of the papers of Mr. James Gayley, on "The Application of the Dry-Air Blast to the Manufacture of Iron," and of Mr. J. E. Johnson, Jr., on "The Physical Action of the Blast-Furnace," by Messrs. Charles B. Dudley, R. W. Raymond, J. E. Johnson, Jr., William F. Mattes, James Gayley, David Baker, John Birkinbine and F. E. Bachman. (Washington Meeting, May, 1905.) CHAS. B. DUDLEY, Altoona, Pa.:-Pam not a blast-furnace man, and this always puts me it a disadvantage because I cannot go into the details of the making of iron and steel. I have not the experience, and have to take the statements of other people, so what I say regarding the subject of this paper is not in the sense of an expert. When I first heard of Mr. Gayley's experiments, I said to myself, " I fear they will result in failure, since, apparently, Mr. Gayley has forgotten one chemical fact, namely, that carbon does not combine with oxygen in the absence of water-vapor." This fact which was so astonishing when it was first brought out some years ago, and which those who are interested may find in the Journal of the Chemical Society of London, for 18S5, page 349, and 1894, page 611, led me to think that the drying of the air would be a mistake. The general subject of the influence of water-vapor on chemical action is a large one; but the special point in which we are for the moment interested, namely, the influence of water-vapor on the combustion of carbon, was especially treated by Mr. H. B. Baker, in the papers referred to. Apparently, however, as the result of Mr. Gayley's experiments, we are to learn that the amount of moisture still left in the desiccated air is sufficient to secure perfectly satis¬factory combustion. In thinking over Mr. Gayley's paper, it occurred to me that there were two alternatives, either of which might be chosen, namely, we might dry the air as Mr. Gayley does, or possibly we might, in a very much simpler way, simply saturate the air at a constant temperature, and thus get uniform working and

Sep 1, 1905

By A. G. Starliper, H. Kenworthy, A. Ollar

Vapor pressure determinations were made on synthesized germanium sulfides. Germanium and cadmium were removed from sphalerite concentrates by fuming. The fume was retreated to separate some of the cadmium from the germanium and, at the same time, upgrade the germanium to more than 5 pet content. MANY sphalerite concentrates contain certain impurities which have economic value as byproducts. These may include the volatile sulfides of germanium, cadmium, and lead. The objectives of the research reported in this paper were to study the fundamental volatility characteristics of germanium sulfides, to increase the recoveries of ger-

Jan 1, 1957

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958

Total U.S. mineral production reached an estimated $17.8 billion for 1960, 4 pct above 1959 and second only to the record high of $18.1 billion established in 1957. As a group, metals achieved a rise from $1.6 billion in 1959 to $2.0 billion this year, an increase of 28 pct. Similarly the value of nonmetallic production including fuels (i.e., natural gas, petroleum, natural-gas liquids, asphalt and related bitumens, carbon dioxide. anthracite. bituminous and lignite coal, peat, and helium) rose from $15.5 billion in 1959 to approximately $15.8 billion in 1960. However, this 2 pct increase in the total value of non-metallic production was due to an increase in the value of the fuels ($11.8 billion in 1959 to $12.2 billion in 1960) which offset a drop in value of the other nonmetallic minerals ($3.7 billion in 1959 to $3.6 billion in 1960).

Jan 2, 1961