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By Everette Lee DeGolyer

FIFTEEN thousand barrels of oil daily, the production of the United States 75 years ago, amounted to more than 90 per cent of world supply. Russia and Romania, neither of which produced as much as one thousand barrels daily, were the only other suppliers in substantial quantity. The adolescent oil industry of the United States, a dozen years old in 1871, was still confined to the Appalachian region. Wells were drilled by cable tools; many of them were "kicked down" by manpower with a spring pole; and depths were measured in hundreds rather than thousands of feet-a 1000-foot well was a deep well. Casing was an innovation, come into general use only a few years previously and still so new as to be subject to bitter patent litigation. Crude oil was packaged in wooden barrels and shipped by flat boat and barge on the creeks and rivers and by railroad. Such pipe lines as existed were only a few miles long. There were many refineries. Pittsburgh, Cleveland and the Atlantic seaboard were refining centers. Refineries were very small, however, and their operations consisted essentially in simple fractionation by distillation and treating for quality. The products in demand were burning oil or kerosene and lubricating oils. Oil was not yet used as fuel and gasoline was a nuisance to the refiner.

Jan 1, 1947

By H. O. Hofman

INSTITUTE OF TECHNOLOGY, In deternlining experimentally the fusibility of clays, two kinds of methods may be distinguished—the direct and the indirect. Of the direct methods, that of Seger has found

Jan 1, 1899

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By Walter J. Johnson

The coals in northern Wyoming and Montana are free-burning and non-caking and range from lignite to bituminous C in rank. Strip and underground mining are employed to supply railroad, utility, industrial, and domestic fuel. The market area includes Iowa, Nebraska, Minnesota, North and South Dakotas, Wyoming, Montana, the Pacific Northwest, and western Canada. THE larger producing coal mines in northern Wyoming are located in the Powder River Basin lying between the Black Hills region of South Dakota, eastern Wyoming, and the Big Horn Mountains in north central Wyoming, see Fig. 1. The mines are located particularly in the area along the route of the Chicago, Burlington & Quincy Railroad from Gillette, Wyo., to a point approximately 15 miles northeast of Sheridan, Wyo. Fig. 2 is a graph of coal production in the state of Wyoming from 1918 to 1951. Across the Big Horn Mountains lies the Big Horn Basin, situated between the Big Horn Mountains and the Rocky Mountains proper. Mining in the Big Horn Basin is almost entirely confined to a small area known as the Gebo Field, near the town of Kirby, which is located on the Chicago, Burlington & Quincy Railroad. This paper will describe present operating areas, making only brief reference to the history of mining and marketing primarily because of the large area to be discussed. The coal beds presently mined in the Powder River Basin are all of Tertiary age and are of Fort Union and Wasatch formations of Paleocene and Eocene ages, see Fig. 3. The Fort Union formation, consisting of 2000 to 3200 ft of alternate sandstone, shale, and coal, is divided from oldest to youngest into the Tullock, Lebo Shale, and Tongue River members. Most of the mineable coal is in the Tongue River member, which is 500 to 800 ft thick. The Carney coal bed, varying from 7 to 20 ft in thickness, is considered the base of the Tongue River member. About 85 ft above the Carney is the Monarch bed, ranging from 18 to 42 ft in thickness. At approximately 210 ft above the Monarch is what is locally known in the Sheridan district as Dietz No. 3 bed, which varies from 12 to 30 ft in thickness. One hundred feet above the Dietz No. 3 is Dietz No. 2 bed, which is 7 to 12 ft thick. At about 100 ft above the Dietz No. 2 is Dietz No. 1 bed, 7 to 15 feet in thickness. Two hundred and fifteen feet above Dietz No. 1 is the Smith bed, approximately 5 ft thick. One hundred twenty-five feet above the Smith is the Roland bed, which is estimated to be approximately 13 ft thick. The Roland bed is considered the base of the Wasatch formation, which in the Powder River Basin is 1000 to 3500 ft thick and is composed largely of shale, sandstone, and coal. The foregoing measures are the only ones above the Tongue River member that have been mined in the Sheridan field. To the east of the Sheridan field, particularly in the area of Gillette, the Roland bed is considerably thicker and is considered the thickest and most extensive coal bed in Wyoming, reaching a maximum thickness of 106 ft. From 125 to 225 ft above the Roland lies the Arvada bed, average thickness 9 ft. Three hundred seventy-five to four hundred feet above the Arvada is the Felix bed, which reaches its maximum thickness of 30 ft near Echeta on the Chicago, Burlington & Quincy Railroad. East of the Powder River the bed averages more than 10 ft in thickness, but it thins in a northwesterly direction. The highest mineable coal in the Powder River field is the Healy bed, about 400 ft above the Felix bed and exposed only in the highest parts of the area where much of it has been burned along the outcrop. Where it has not been burned, the thickness at most of the outcrops is 10 to 15 ft.

Jan 1, 1954

By A. K. Mukherjee, J. E. Dorn

A modified Peierls model is Presented for the rationalization of the asymmetric plastic behavior of single crystals of bcc metals. The model assumes that the asymmetry of slip arises from a tendency toward asymnetric splitting of the a/2[111] screw dislocation. The approach differs from former theories however insofar as it assumes that the splitting is so minor ttut only the core energy is modified and that no real partial dislocations exist. As a consequence, the concepts of a line energy of a partial dislocation, interaction between partial dislocations, constriction energies, and stacking fault energies are not invoked. Instead the present analysis is based on a specialization of the Peierls mechanism which assumes an asymmetric dislocation core which is modified by the effective stress and permits cross slip. The theoretical predictions on the stress-temperature -strain rate and orientation relationship agree qualitatively with the limited experimental data that are currently available. Additional experimental work over wider ranges of conditions is suggested to provide more complete evaluation of the possible validity of this theory. RECENT experimental investigations on the low-temperature thermally activated deformation of bcc metals have confirmed the existence of several unique orientation effects. These will be described with the aid of the standard stereographic projection shown in Fig. 1. If slip were determined exclusively by crystal symmetry, the deformation characteristics would be symmetrical about X; = 0 and independent of whether the specimen were subjected to a tension or a compression stress, regardless of what combinations of slip planes might be operative. Experiments, however, reveal that neither of these symmetry based predictions are valid. A schematic representation of the commonly observed asymmetry of both the yield stress and the plane of slip is shown in Fig. 2. A reversal of the direction of stressing results in an inversion of the asvmmetric behavior. 1) Asymmetry bf Yielding. A detailed investigation on the asymmetric yielding in an Fe-2.7 pct Si alloy was repoEted by Tabka, Tikeuchi, and Furubayashi,1 Similar trends have been observed by Keh and Nakada on iron,' Stein on molybdenum,3 Bowen, Christian, and Taylor4 on columbium, Sherwood, Guiu, Kim, and pratt5 on Ta, Cb, and Mo. The degree of asymmetry not only depends on the atomic number and alloying but, in all cases that have been examined, it also increases with a decrease in the test temperature. 2) Asymmetry of the Slip Plane. Asymmetric $I-~: curves of the type shown in Fig. 2 have been found for several Fe-Si alloys6-8,1 and columbium.4 There is general agre_ement that near X: = 30 deg slip occurs by the [111](211) mode so that ?1 = 30 deg. As X; decreases it appears that [111](211) to [111](101) cross slip takes place leading to slip band traces on intermediate planes. And as xi approaches 0 deg, sharp

Jan 1, 1970

By H. D. Newell

THERE has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-tem-perature steels" are meant those specifically designed for service at ele-vated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service.

Jan 1, 1937

By C. S. Barrett

THE crystal imperfections known as faults in stacking (stacking disorder) are of importance to both fundamental and applied science and are receiving increasing attention. On the theoretical side there have been recent advances in the analysis of diffraction patterns in terms of stacking faults, and on the experimental side it has been found that certain metals develop a faulted structure on cooling through a phase transformation. Beyond this, little is known of what may be called the physical and mechanical metallurgy of faulting, although there has been no lack of discussion and conjecture as to the presence of faults in metals and the effect of faults on mechanical properties and microstructures. In the close-packed metals the nature of faults can be described very simply. Face-centered cubic (FCC) crystals consist of close-packed layers of atoms, (111) planes, stacked above each other in a definite manner. If one layer is designated as the A layer, the next must be a B or a C layer; that is, every atom of the second layer lies not above the atoms of the A layer, but nestles in the hollows between these, using the hollows designated as the B positions, or the equivalent hollows designated as C. If the sequence of layers is ABCABC...., so that layers three spacings apart are directly over each other, the crystal is FCC; if CBACBA ... it is an FCC crystal that is a twin of the former; if ABAB........or BCBC..it is hexagonal close-packed (HCP). A fault is a break in the sequence, such as ABCABABC .. . which has the effect of inserting an HCP lamella into an FCC crystal. Regularly spaced faults spaced two layers apart would convert an FCC crystal entirely to HCP, or an HCP to FCC. A fault in an FCC crystal is also equivalent to creating an FCC twin of minimum thickness; in fact, the entire crystal would be converted to its twin if faults were introduced regularly. (In HCP crystals, however, twinning does not occur on the basal plane and a fault on this plane is not identical with a thin twin). Faults are one of the possible causes for annealing twins,' for the strain markings that are brought out by etching deformed metal,'," for the altered X ray reflecting power of metal at slip bands that is revealed in X ray reflection micrographs,' for the extinction of Kikuchi lines in electron diffraction patterns, and for the hardening of latent slip planes.' Since other explanations of these effects are also available," there has been no direct proof of faults from deformation; yet it has appeared likely that they would occur. Faults resulting from phase transformations in metals, however, have been clearly revealed by diffraction in cobalt" and lithium. It is to be expected that the faulting tendency is greatest

Jan 1, 1951

By R. J. P. Lyon, A. E. Prelat, H. Lawrence

Introduction In 1977, the US Bureau of Mines awarded a grant to the state of South Carolina to explore the possibility of using Landsat multispectral scanner (MSS) data as an aid in monitoring surface mining activities in selected counties of the state. Work had been done in Aiken County prior to the grant by USBM and state personnel at the EROS Data Center using both the GE Image 100 and ESL IDIMS systems. The initial work on the 1:100 consisted of locating and measuring the areas of various kaolin mines. The results were excellent on location, identification, and accurate area measurements of several mines as compared with aerial photos of each mine. The effort also included locating and measuring the size of all mines (including sand and gravel) within two US Geological Survey (USGS) 7 % - min quadrangle maps. Line printer overlays using the IDIMS equipment and software resulted in the location of all known mines within an estimated error less than zt 91.4 m. Mine acreage was calculated by counting each symbol (which represented one pixel) and multiplying by 1.1 (the number of acres per pixel). [Fig. 1] shows a portion of one quadrangle overlay. [Table 1] gives a comparison of acreage measured for several mines from the 1-100 and IDIMS system vs. aerial photo measurements. The success of the preliminary work resulted in the South Carolina Land Resources Conservation Commission submitting a proposal to USBM for funding to expand the scope of work to other mineral mining operations within the state and determine if Landsat Imagery could be used to accurately locate and measure mining and reclamation activity on a continuing basis. Three separate tasks were proposed for selected kaolin mines in Aiken County: Task 1, to measure changes in active mine developments over the period 1974-77; Task 2, to measure reclamation activity, and, if time permitted, seasonal changes in mine signatures over the same period of time; and Task 3, to classify one complete mining operation (i.e., differentiate between active, spoil, overburden, water, reclaimed portions and surrounding terrain. The major effort was centered around J.M. Hubeis Richardson mine. Mining operations were progressing in a northerly direction and included three areas of reclamation: one prior to 1974; one started during early 1974; and one reclaimed during 1976. A discussion of all work done under the grant is available in the March 1979 Final Report listed under References. Computer compatible tapes (CCTs) containing MSS data from Landsat Path 18, Row 37, were purchased from the National Aeronautics and Space Administration (NASA) covering the period February 1974 through January 1977. The MSS data were processed on the General Electric Image 100 using parallelepiped classification at the EROS Data Center's Data Analysis Laboratory, Sioux Falls, SD, and at the Stanford Remote Sensing Laboratory, Stanford University, Palo Alto, CA, utilizing both an unsupervised classification (ISOMIX) and a supervised classification (sequential discriminant analysis). Studies at Stanford University Remote Sensing Lab (SRSL). In Feburary 1977, initial work was begun at Stanford using the STANSORT computer program running on a DEC PDP-10 (Honey, Prelat, and Lyon, 1974). This software is fully interactive and designed to study Landsat CCT data at high resolution (small areas) on a pixel-by-pixel basis (Lyon, 1977). Unsupervised Classification. The initial step was to locate the Richardson mine on the positive print of the full Landsat scene from CCT 1644-15252, dated 6/17/74. This was relatively easy due to a large abandoned kaolin mine and a long narrow pond clearly visible in the scene. Two unsupervised classifications of the Richardson mine were run using ISOMIX clustering (Honey, Prelat and Lyon, 1974). (ISOMIX essentially follows the interactive clustering procedures of ISOCLS Kan, Holley, and Parker. 1973). Although the classifications were successfully accomplished, it was apparent from the TV display that the results did not clearly define the mine areas. A supervised classification would have to be made in order to clearly separate each portion of the mine. Supervised Classification. This classification was done using the Stepwise Discriminant Program (BMDO7M) which is part of the BIOMED package (Dixon, 1970) and involved the following steps: Training group populations were selected and the digital

Jan 1, 1982

In late May, at its final session in Nairobi, Kenya, the UN Conference on Trade and Development (UNCTAD) narrowly rejected the US proposal for a new International Resources Bank suggested by Secretary of State Henry Kissinger. The proposal was defeated by a roll-call vote of 33 to 31, with most of the nay votes cast by communist countries, and with 89 of the less-developed countries abstaining or absent.

Jan 7, 1976

By Ralph Hultgren

FEW phase diagrams of alloys composed of two transition metals have been adequately studied, probably because of the high melting points involved. Transition metals are the elements that have inner shells incompletely filled with electrons. They comprise groups IIIa to VIIIa of the periodic table, including more than half of all metals. We have chosen to study two systems whose comparatively low melting points allowed the alloys to be melted in a molybdenum resistance furnace. The nickel-palladium system proved to consist of a simple series of solid solutions, but iron-palladium manifested several remarkable features. The main characteristics of the latter diagram were decisively established, but lack of time prevented precise determination of phase boundaries. The gamma to alpha transformation in this system is unusual and warrants further study. Grigorjew1 determined the liquidus and solidus of the iron-palladium system by thermal methods. He found a minimum melting point, but no eutectic. He also found that palladium lowered the gamma to alpha and raised the gamma to delta transformation temperatures of iron, with a complete series of solid solutions existing between gamma iron and palladium. His measurements also indicated a compound or super-lattice near the composition FePd3. Jellinghaus2 found that annealing at 500° C. greatly increased the magnetic coercive force of an alloy of composition FePd. X-ray dif-fraction photographs showed that a tetragonal ordered phase had formed during the anneal.

Jan 1, 1939

By H. M. Chance

In the early part of 1893, I had occasion to make for the owners a professional examination of the Rich Patch tract; and, with their permission, I present in this paper, omitting the commercial portions of my report, those portions which may be valuable to future students of that region. Location, Topography And Geology. The Rich Patch tract comprises about 9000 acres, located about 3 miles west of Low Moor, on the Chesapeake and Ohio Railway, in Alleghany county, Va., and immediately adjoining the Low Moor property. In shape the tract is roughly quadrangular, being about 3 miles broad in a northerly and southerly direction, by about 6 miles long from east to West. Potts creek and Jackson river run along its northern boundary. It is drained by Hayes Gap run, Mill branch and Laurel creek, which flour north into Potts creek, and by Karnes creek, which flows northeasterly through the Low Moor property into Jackson river. The topography of the tract is shown by the accompanying map (Fig. I), and need not be described here. The valleys are cut down from 1000 to 1500 feet below the mountain summits, which generally reach an altitude of about 3000 feet above tide. The geological structure of the district is indicated by the geological cross-sections shown in Figs. 2 and 3. These sections show that the formations underlying the property extend from the Lower Silurian lin~estones up to the Devonian slates, including the numbers of the Paleozoic system of rocks as defined by the geological surveys of Virginia, Pennsylvania and New York, from No. 11. to No. VIII. • No. IX. Old Red Sandstone, No. VIII. Slates and Shales, Devoman-

Jan 1, 1900

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By W. D. Forgeng, P. F. Wieser

MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.

Jan 1, 1964

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By R. S. Busk, R. F. Marande

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By R. F. Marande, R. S. Busk

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By H. M. Day

THE constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were con-firmed and supplemented through X-ray analyses by Preston and Stenbeck.3 According to Murphy, at 276° C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower tempera-tures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region.

Jan 1, 1938

By J. E. Hilliard

Various methods are given for estimating the number per unit volume and average size of convex particles from measurements on a projection through a slice of the structure. The determination of the size distribution is considered specifically for spherical particles. The results are applicable to any type of transmission microscopy and also to the correction of measurements made by reflected light on semitransparent materials. WITH the advent of electron transmission microscopy, the metallurgist is confronted with the problem of relating a projected image to the three-dimensional properties of the structure. This paper deals with the estimation of the number per unit volume and size of particles dispersed in a matrix. The case of convex particles will first be treated (the results will be applicable as approximations to particles of more general shape) and then spherical particles will be considered specifically. The latter represent a special case frequently encountered in practice and one which is also amenable to a calculation of the effect of overlap on the observed particle-size distribution. Although the present treatment was prompted by the needs of the electron microscopist, the results are applicable to transmission studies with any type of radiation. In addition, they can be used in the analysis of semitransparent materials by reflected light, the depth of light penetration corresponding to the thickness of the slice or section used in the transmission studies. 1) CONVEX PARTICLES 1.1) General Expression for N,. We will suppose that a "center" (such as the center of mass) is assigned to each particle. The convention used for defining the center is immaterial providing it does not depend on the orientation or location of the particle. Consider a slice through the structure having a pair of parallel faces a distance t apart. It will be assumed that the slice is randomly located with respect to its perpendicular distance from some fixed point, but it is not necessary to assume that its orientation is random. Our problem is to deduce the relationship between the number of par- ticle images seen on an orthogonal projection through the slice with the number, Nv, of particles per unit volume in the original structure.* *Symbols are listed in the Table. The expected number of particles with centers lying within the slice is Nvt per unit area. In addition, there will be elements in the slice contributed by particles whose centers lie without. The number of such elements will be the same as the number of intersections occurring on a two-dimensional plane through the structure; namely N~K, where K is the mean distance, Fig. 1, between tangent planes to a particle averaged over all particles, i.e., Where Ni is the number of particles of class i having the same shape and size, and pi (4, 8) is the probability that an i particle will have a given orientation with respect to the slice. If the particles are randomly oriented, then K is independent of the orientation of the slice and equal to the mean cali-per diameter. The total number of particle elements in the slice is therefore Nv(t + K) per unit area, but fewer will be seen as separate images on the projection plane because of overlap. If MA is the number of elements "lost" by overlap, the number of images per unit area will be NA = Nv(t + K) -MA 121 MA is a function of the slice thickness and must vanish at t = 0. As t increases, NA at first increases, reaches a maximum, and thereafter decreases as the overlap term MA becomes predomi-

Jan 1, 1962

On August 22, 1966, just 20 months after writing sales agreements with Japanese steel mills, Hamersley Iron Pty Ltd made its first contractual shipment of 52,000 tons to Yawata Iron and Steel Co Ltd. As world news, the event was not spectacular. But to mining men it represented an astonishing achievement. Twenty months of feverish effort and the expenditure of more than $100 million had created a large open-pit iron ore mine, a crushing plant, storage and load-out facilities for sized ore, and a supporting township at Mt Tom Price; a 182-mile standard gauge railway; and port and loading facilities for a nominal loading capacity of 6000 tph as well as a port town, Dampier, on King Bay. The project was executed in the sparsely inhabited, arid, dissected-plateau country of the Hamersley Range in the northwest sector of Western Australia. Hamersley, 60% owned by Conzinc RioTinto of Australia Pty Ltd and 40% by Kaiser Steel Corp, holds sale contracts for ore and pellets valued at $770 million. The main contracts are with the Japanese, who are to be supplied with 65.5 million tons of ore during the 16 years from August 1966 to August 1982 and 18 million tons of pellets over a 10-yr period beginning in early 1968. Of lesser importance at this time, but presaging trends, are contracts for a total of nearly 1.5 million tons to be shipped to England and Western Europe during the years 1966-68. A pellet plant with a capacity of 2 million tpy is now under construction at Dampier and is to be on stream early next year. Another interesting project for which the plans are set, is a desalination plant for sea water to supply industrial requirements and potable water for the town of Dampier.

Jan 5, 1967