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By David B. Reger

Oil and gas and their derivatives continue to be stable products in West Virginia. In the midst of the cataclysmic happenings of 1930 to 1934, which have swept away banks and practically destroyed many other enterprises of presumably nonspeculative character, the possession of a royalty or working interest in a few old oil or gas wells has prevented disaster in literally thousands of homes. These old wells yield their daily quotas of basic commodities, which the public must have. Fortunately, the facilities of disposal in the Appalachian Province are so ample and well managed that the owner of such equities may be reasonably certain that his proportionate share of existing markets will be afforded him without much effort on his part. In most cases these investments are free from encumbrance or hypothecation, therefore the main uncertainty is the date of ultimate exhaustion at the source. Generally, this is known to be fairly remote. The net result has been that individual owners part with such investments only as a last resort. In sharp contrast to the action of the small owner of wells or royalties who has prudently refrained from jeopardizing his rather certain income by drilling new wells that may be failures, or of which the product may not be needed for the moment, has been the plight of various promotional enterprises in natural gas. Many of these ventures have been operated by amateurish remote control and practically all have been overloaded from the start with bonds and debentures, which could only be satisfied in a rising and expanding market; and with operating costs that have been exceedingly high because of widely scattered producing units and large overheads. Many of these promotions are now in receivership or bankruptcy and in various instances the original units have been recaptured by former owners and have again become profitable by reason of personal operation and elimination of all forms of overhead expense. New Development In 1934, the State issued 524 permits for drilling. According to the trade journals, 553 wells were completed, with 184 oil wells, 274 gas wells and 95 dry holes (Table 3).

Jan 1, 1935

By E. C. Potter

It is not the purpose of this paper to enter into the minutiae of a subject so vast, upon which volumes have already been written and volumes more might still be written, but simply to pass in review the characteristic features of that practice, which, dating from the blowing-in of the Edgar Thomson "A" furnace in 1879 and continuing down to the present day, has given to American blast-furnace operations a new significance. The blowing-in of " A" furnace marked the beginning of a new era in the science of iron-smelting if, indeed, it was not the very birth of science as applied to this industry in the United States. American blast-furnace practice in its generic sense and world-wide significance dates from that day, and really all that is valuable, all that is remarkable or worthy of discussion, is embraced in the experiences and achievements of the past fifteen years. Back of that we find only the dead level of mediocrity, or worse, a dispoition to " let well enough alone;" a general, almost universal, employment of " rule of thumb " methods. The application of scientific principles and methods was rare and, indeed, previous to the introduction of the Bessemer process in the early seventies, science had no place in controlling the operations of the American blast-furnace. The old practice consisted mainly in dumping raw materials in at the top of the furnace and tapping out iron and slag at the bottom, for the successful consummation of which the furnace-manager directed his best energies toward keeping the furnace as free as possible from "gobbing" with, alas ! but indifferent success. The burdening of the furnace was based largely on Mark Twain's receipt for " Johnny-cake," altered to suit the circumstances, viz.: a lot of ore, a lot of fuel and about a quarter of a lot of flux. The possible capacities of furnace-plants were not nearly realized. Enormous wastes were permitted, unheeded because not understood. In the use of fuel quantum suff. was always the rule. Increase of product was not thought of because it was not deemed wise or safe to attempt

Jan 1, 1894

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET's and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.' More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET's. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET's with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By L. J. Dijkstra, R. J. Sladek

IN earlier work the effect of manganese on the general behavior of nitrogen in iron was the subject of a careful examination by Fast.' Part of the investigation was made, in collaboration with one of the present authors (L.J.D.), by using the internal friction method. This technique, which has been described elsewhere,' showed some significant changes in the properties of Fe-N alloys by the addition of a small amount of manganese namely: 1—Under standard conditions the maximum of the nitrogen peak in pure iron appears around 20 °C and the half width is about 27 °C. By addition of 0.5 atomic pct Mn a general broadening of the internal friction peak occurs. The half width is increased by about 9°C. Moreover, a shift of the maximum of about 5°C toward a higher temperature takes place, Fig. 2. 2—The precipitation of nitrogen from the supersaturated solution, measured, e.g., at 200 °C, was inhibited by the addition of the amount of manganese given in effect 1. The broadening of the nitrogen peak was confirmed in more recent work3 on samples which were prepared from Westinghouse Puron iron. The effect of manganese on the rate of precipitation, however, was much less striking than in the earlier work' based on Philips high purity iron. Theory To explain the first change in properties just referred to, effect 1, the following two assumptions were made:' First, every manganese atom in sub-stitutional solid solution creates around it six interstices located between an iron and a manganese atom, as is evident from Fig. 1. These interstices, conveniently called Fe-Mn interstices, have for nitrogen a free energy level which is AG* lower than the normal Fe-Fe interstices between two iron atoms. For such low concentrations of manganese as 0.5 atomic pct, the possibility that two manganese atoms will be nearest neighbors can be disregarded. Second, it is assumed that in addition to the normal relaxation time TFe at least one new relaxation time, Mn, Fe, enters in the phenomena which is associated with the elementary diffusion jumps between a Fe-Mn interstice and an adjacent Fe-Fe interstice. Fig. 1 gives schematically the free energy for a nitrogen atom as a function of its position along the line ABC. A tentative analysis of the nitrogen peak in a 0.5 pct Fe-Mn alloy based on these assumptions has been made in Fig. 2. The dotted curve with a maximum at 22°C is caused by jumps between Fe-Fe interstices, the dotted curve with maximum at 32°C by jumps between an Fe-Mn and an Fe-Fe interstice. The two effects added together give the dash-dot internal friction curve for the alloy. In the following these two components will be referred to as the normal peak at 22°C and the abnormal one. (The small secondary peak at

Jan 1, 1954

By Hermann Bach, Walther Hänig, Willi Gehrhardt, Ernst Theurich, Walter Langner

With the construction of the Magdeburg zinc works, the Georg von Giesche's Erben Mining Co. of Breslau has to a certain extent completed the program of reconstruction which it set as its goal after the boundaries of Upper Silesia were drawn by the Treaty of Versailles. During its history, covering.more than two centuries, zinc and lead mining has been its chief activity. Through the new boundaries established, it lost to Poland all its mines and smelters, including five distillation smelters. Of its extensive properties, there remained only an apparently unimportant and unexplored portion of the old Bleischarley ore field which, however, happily made possible the resumption of its old business. In 1925 the Deutsch-Bleischarley shaft-only a few kilometers from the old Bleischarley shaft—was sunk and developed, and in May 1926 production of lead and zinc ore was resumed. As facilities for smelting were lacking, the ore was at first delivered to the neighboring smelters, which had now become Polish. Realization of the plan to build its own zinc works had to be postponed at first for lack of capital. In the meantime, however, plans for the new works were worked out in all details. After extensive experimentation in a semicommercial pilot plant it was decided, at the end of 1928 and the beginning of 1929, to use the electrolytic process and, for economic reasons, to place the works at Magdeburg. With zinc at the approximate price level that had ruled since the Deutsch-Bleischarley mine had begun working, it was hoped that the plan could be completed in 1930 with the company's own resources. However, falling metal prices, already noticeable in 1929, made this impossible, and further postponement for a time became necessary. Finally, at the end of July 1933, the funds for building the works became available, in the form of a loan granted under the first employment

Jan 1, 1937

By J. L. O’Brien, M. Suenaga, K. M. Ralls, V. F. Zackay

The effecls of aging a1 400°C on tile resistive transition at 4.2°K of a superconducling 70Zr-30Nb alloy are reporled. Microstrclural changes were studied by critical temperature, resistiue critical field, residual resistiuily, and microhardness measurements and by X-ray diffraction, optical microscoby, ad replication electron microscopy. The result of the aging treat- A defect-free Type 11 superconductor in a magnetic field above Hc1 cannot sustain a transport current runt is a fine array of w-phase pavticles with a mean center to center interparticle spacing of about 800A. At an aging time of 300 hr the maximum onset critical current density is rcached. The particle size at the maximum current density if about 4202. At times longer than 300 hr effective particle impingement leads to lower onset critical current densities. perpendicular to the applied field without power loss in the sample.'-3 This power loss is due to flux line motion caused by the Lorentz force and is manifested by a longitudinal voltage.4-6 When defects are present in the material, flux lines are pinned until the Lorentz force exceeds the "pinning force". That is, it is thought that flux lines reside in free-energy wells existing at the defects, and the critical Lorentz force is that which when integrated over distance will supply the free-energy difference necessary to move the flux

Jan 1, 1968

By George Mansfield

INTEREST in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lake-land, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.1 At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern pro-ducers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This informa-tion has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,2 some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,3 of the Tennessee Division of Geology. Prof. J. Stewart Williams,4 of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered.

Jan 1, 1940

By AIME AIME

ADDRESSING the Ohio Section at a recent meeting in Columbus, Ohio, R. C. Allen, executive vice-president for Oglebay, Norton & Co., Cleveland, spoke on "The Iron-Ore Industry of the Lake Superior Region in Prosperity and Depression." The speaker considered this region in connection with the problem of national security. This is the age of minerals; progress depends on them; and next to agriculture, the mineral industry is of prime importance. The United States has no shortage of minerals rather an over-supply; but many mines have been and are being exhausted. The shifting of the sources of supplies of minerals so important as copper, petroleum, and iron to other countries would create internal strains and affect international relations. There will be no early decline of ore mining in the Lake Superior region unless it is forced by unwise public policies. Iron ore is industrial strength and self-sufficiency. A study of economic geography is important for statesmen and mining men, because the minerals essential for peace and war are haphazardly or irregularly distributed throughout the world. Of these minerals, 75 per cent are owned by 10 per cent of the population, mainly peoples of Anglo-Saxon origin.

Jan 1, 1934

By NATHANIEI HERZ

(Cleveland Meeting, October, 1912.) THE formula very frequently used for computing the economical size of pipe to transmit compressed air is that of D'Arcy, as follows: d5(p1-p2)/w1l D-c w11 Where, D = the volume of compressed air delivered in cubic feet per minute,-at the final pressure. c = an experimental coefficient determined for the various sizes of pipe. d = the diameter of the pipe in inches. 1 = the length of the pipe in feet. P1 = the initial gauge-pressure in pounds per square inch. p2= the final gauge-pressure in pounds per square inch. W1 = the density of the air, or the weight in pounds per cubic foot at the initial pressure, p,. The most common case is that in which the given quantities are: the quantity of air required, the length of the pipe, and the initial pressure. The method of solution is to assume a pressure-loss and to compute the remaining factor, c/d5, thus giving the size of pipe corresponding to the assumed loss of pressure. It is always desirable to try two or more pressure-drops, in order to find the combination that is most satisfactory, since often a small change in the size of pipe will reduce or increase the loss of pressure several pounds. An alternative method is to assume a size of pipe and calculate the corresponding pressure-drop. Each method involves a series of tedious calculations to arrive at the most economical solution, and also requires the use of tables giving the constant, c, the actual diameters corresponding to the nominal pipe-sizes, the density of the air, w1, and often, for convenience, a table giving the

Dec 1, 1912

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

J. D. Fast and J. L. Meijering (Philips Research Laboratories, N. V. Philips' Gloeilampenfabrieken, Eindhoven, Netherlands)— After the departure of our friend Dijkstra to the United States, investigations on the effect of alloying elements on the behavior of nitrogen in a iron were continued in Eindhoven. We too found internal friction curves with two separate peaks for iron containing nitrogen in addition to 0.5 atomic pct V or 0.5 atomic pct Mo. Our first publication on these investigations" appeared almost simultaneously with the paper now under discussion. At first sight our experimental results seem to be in harmony with their conclusions, but a closer examination reveals that in the case of the Fe-V-N alloy the abnormal peak is not controlled by one time of relaxation only. Whereas iron containing 0.5 atomic pct Mn or Mo absorbs an amount of nitrogen of about the same magnitude as that absorbed by pure iron under identical conditions, iron containing vanadium absorbs in addition one nitrogen atom for every vanadium atom. This last amount, far exceeding the first amount in the case under consideration, combines chemically with the vanadium and causes no internal friction. The "free" nitrogen in the vanadium alloy gives rise not only to a damping peak corresponding to that in pure iron but— due to the presence of VN particles in the metal—also to the abnormal peak at higher temperatures. The VN particles create interstitial sites around themselves where the free nitrogen atoms are bound much tighter than in the normal interstices. These abnormal interstices, therefore, will capture free nitrogen atoms rapidly, whereupon these give rise to the abnormal damping. The binding energy in the abnormal interstices is not the same for all, and with coarsening of the VN precipitate the distribution of these energies is displaced toward the side of stronger binding. This is deduced from a shift of the summit of the second peak toward higher temperatures (from 80" to 88°C in our experiments) caused by prolonged heating at 950°C. From the intermediate state where they cause the abnormal damping, the nitrogen atoms pass over rather rapidly into the fully precipitated state (iron

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