Search Documents

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

Jan 1, 1967

By Douglas D. Donald

The New Jersey Zinc Co. successfully holed through a 2 1/2-mile haulage tunnel connecting its new Ivanhoe shaft with the Van Mater Shaft at Austinville, Va. This 8x 10-ft cross-section tunnel was driven from both ends and met at a point approximately a mile from one shaft and a mile and a half from the other. In order to make certain that the faces met accurately on line and grade it was necessary to refine conventional mine surveying practices. The mines that are serviced by these shafts are located in the southwestern part of Virginia approximately midway between Roanoke and Bristol at the west foot of the Blue Ridge. While the presence of lead-zinc sulfide ores has been known in this area for more than 200 years, it was in 1902 that New Jersey Zinc Co. acquired the Austinville property, which has been in constant operation since that time. About ten years ago the company undertook an extensive diamond drilling program at Ivanhoe several miles to the southwest. This program was successful in locating sufficient ore to justify the purchase of a number of the properties in this area and plans were made to develop the new orebodies. The discovery of this ore as well as substantial addi- tional reserves at Austinville resulted in a decision by the company to increase its daily milling capacity to 3000 tons, of which about 1000 tons would be supplied from the Ivanhoe mine. After careful consideration of all possible methods of transporting this volume of ore from Ivanhoe to the mill, it became evident that diesel locomotive haulage through a 2½-mile tunnel between the two mines would best suit prevailing conditions. Since the lowest operating level, known as the 1100 level, of each mine would be at approximately the same elevation, it was obvious that such a tunnel should be driven on this level. Not only would this tunnel facilitate feeding Ivanhoe ore into the underground crusher and skip loading installation at Austinville, but it would also open up a known orebody 5000 ft southwest of the Van Mater shaft. In addition it would provide a valuable diamond drilling base from which a large and a potentially favorable but untested block of ground might be explored. In order to hasten the completion of the tunnel, it was felt that it should be driven from both ends. ENGINEERING CONTROL PROCEDURES It was vital that the tunnel junction be made accurately on line and grade; thus it was felt that engineering control of an unusually high degree of reliability was required to prevent an accumulation

Jan 1, 1959

By K. K. Landes

The north central and northeastern states supply over 50 pct of the chemical and metallurgical limestone produced annually in the United States, and Ontario is the leading source of this material in Canada. About three fourths of the chemical and metallurgical stone produced in this area comes from Michigan, Pennsylvania, Ohio, and Ontario. The specifications, physical and especially chemical, for chemical and metallurgical stone depend upon the end use, but in general the tolerance for impurities is so low as to rule out most limestones and dolomites. Both high calcium limestone and dolomite are used in the metallurgical and chemical industries. The principal metallurgical use is as a flux in iron ore blast furnaces and open hearth steel furnaces. The major chemical uses are in lime burning and soda-ash manufacture. Other important uses include glass manufacture, in making calcium carbide, and in sugar factories. All deposits of high quality carbonate rock are definitely finite. Invariably and inevitably they diminish in either thickness or quality laterally so as to become unworkable as chemical and metallurgical stone. The size of these high quality lenses ranges from a few thousands of tons to hundreds of millions of tons. The best hunting for new supplies is in the geologic formations known to contain premium quality deposits. However, because of high transportation costs, carbonate rocks, to be workable, must be close to market, dollarwise. Definitions: Chemical stone is limestone or dolomite used as a raw material by the chemical industry. The major chemical uses are in lime burning and soda-ash manufacture. Other important uses include glass manufacture, making calcium carbide, and in sugar factories. The specifications for chemical stone depend entirely upon the end product. Some uses require dolomite, some require high calcium limestone; in a few instances, notably in lime burning, either type of carbonate rock can be used as raw material. As a general rule, a fairly pure stone is necessary and for certain particular uses the tolerance for some elements such as sulfur, iron, and phosphorus may be extremely small. Metallurgical stone is used as a flux in furnace operations, especially in the blast furnace where iron ore is converted into pig iron and in the open hearth furnace where pig iron is made into steel. Either limestone or dolomite can be used in the blast furnace, but only high calcium stone is charged in the open hearth (except for rice-size dolomite used as a refractory). There are no rigid chemical specifications for blast furnace stone, but low silica, alumina, sulfur, and phosphorus are desirable. For open hearth use, in addition to low magnesia, a very low sulfur content is also specified by many furnace operators. For furnace use, fluxstone also must be sufficiently shatter resistant that it will remain in lump form during transport and charging into the furnace. Commercial stone is the term applied in the trade for crushed stone used for roadstone and in concrete aggregate. Many of our best chemical and metallurgical limestones are too soft to qualify in the Los Angeles abrasion test for use as commercial stone. However, some limestones, and a higher proportion of dolomites, do qualify for commercial stone and so can be sold to either market. Place Value: Even the highest grade limestone is still a bulk commodity with a relatively low value per ton. As a matter of fact there is very little difference in the average price per ton between high grade chemical and metallurgical stone and crushed limestone used commercially. Most high quality stone is produced in large operations with consequent low cost per ton whereas most commercial stone is produced in relatively small local quarries. As in the case of other bulk commodities most limestone buyers pay more for transporting the raw material than the cost of the stone at its source. For this reason steel furnaces and chemical plants

Jan 1, 1961

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957

By Harold Price

ONE year ago, that is in January, 1923, there had not been constructed a single oil-storage tank of 55,000-bbl. or more capacity with a completely electric welded roof and bottom. Today, there are at least fifty 80,000-bbl. storage tanks completed, or nearing completion, on which both the roofs and the bottoms are electric welded. It is the purpose of this paper to describe, in a general way, the construction of these FIG. 1.-ELECTRIC-WELDED SEAMS AND RIVETS OF BOTTOM IN 55,000-BBL. TANK AT EL DORADO, KANS., SHOWING ALSO PATCH PLATE WELDED TO BOTTOM. welded roofs and bottoms, and to give their advantages over riveted construction. All of the following data and conclusions were obtained from observations made during the welding of tanks by the Welding Engineering Co. at Texas City, Tex., and Tonkawa and Burbank, Okla. As far as can be determined, the first electric welding on large tankage was completed in May, 1922. At that time the Empire Companies of Bartlesville, Okla., discovered a badly leaking bottom in a 55,000-bbl. tank at El Dorado, Kans. They had considered concreting this bottom, but because of the much smaller cost, decided to try electric welding; so a- contract was given the Welding Engineering Co. of Bartlesville, Okla. In this instance, no new sheets were added, the bottom being repaired by electric welding of all seams and rivets, Fig. 1. In some places where the original rivets were missing, the holes were filled by welding; patch plates were also added at certain badly worn spots. This tank has since been in service over a year and half, but no other

Jan 6, 1924

By L. W. Pommier, F. B. Brien, A. K. Bhasin

In the field of mineral processing, although many operations are applied to suspensions of ore particles in fluids, there is a lack of fundamental knowledge relative to the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. Previously proposed equations, based on the Ostwald-de Waele (power-law) model for non-Newtonian fluids, are exam ined in the turbulent flow region relative to a number of pertinent variables and their effects on the movement of immersed bodies. As more knowledge is acquired in regard to the effects of suspension variables on the rheological properties, useful relationships may be proposed to allow predictions of conditions to achieve optimum results for engineering purposes. In the field of minerals processing, many operations are applied to suspensions of ore particles in fluids. The differential movement of solids of various sizes and densities in suspensions is of utmost importance to gravity concentration, wet classification, flotation, hydrometallurgy, and pipeline transport of solids. The subject is also of importance to other branches of engineering; for example, those involved with soil mechanics, ceramic slips, and oil-well drilling fluids. There is a lack of fundamental knowledge relative to the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. The problems encountered in the direct application of the well-known Stokes and Newton's Laws to non-Newtonian systems have been examined in a previous paper.' Equations were proposed based on the Ostwald-de Waele (power-law) model for non-Newtonian fluids. This present paper examines these equations in the turbulent flow region relative to a number of pertinent variables and their effects on the movement of immersed bodies. It is thought that, as more knowledge is acquired as to the effects of suspension variables on the rheological properties, useful relationships may be proposed to allow prediction of conditions to achieve optimum results for engineering purposes. The purpose of this paper is to make an initial assessment of the nature and magnitude of pertinent suspension variables. In order to avoid too voluminous a document, the examination of kinetics and mechanisms will be omitted at this time. THEORY A Newtonian fluid is defined as a fluid in which the stress is proportional to the rate of strain, 2 i.e.: H = viscosity; see Table I. for list of symbols The following equations are conventionally used to assess the motion of spherical particles moving under laminar and turbulent flow conditions through Newtonian fluids: When these relationships are applied in practice to suspensions, the liquid density is substituted by a composite suspension density, and viscosity is usually taken as that of the suspending liquid or an approximated "apparent viscosity." However, suspensions are non-Newtonian in character3 and thus, more than one viscosity parameter is required to describe their behavior. A number of models have been proposed for non-Newtonian fluids;2,4 among these the simplest is the Ostwaldde Waele or power-law model for incompressible fluids which for one dimensional flow may be reduced to:

Jan 1, 1970

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By Charles Hart

In this paper it is the author's intention to show the extent and character of foreign ores now known to be available; these deposits may be in active production or held in reserve until economic conditions may make them active. He hopes to show the relation existing between these ores and the American supply, and which of the former are now producing or will in turn come into production when our better ores have been exhausted. This phase of this discussion must of necessity include some data as to the present rate of consumption and a study of the changes we may expect here and abroad in the general steel trade and its sources of supply in raw materials. It is obvious that the occurrence of coal, ore and limestone in relation to one another and the proximity of a market are the elements in control of this feature of the problem. If the foregoing situation is favorable, all the other questions may be solved, for it is clear that with proper basic conditions finance, labor and operations will fall in line. We present a short outline of the present methods of carrying on the foreign iron ore trade, believing that it is of general interest in comparison with our own highly specialized methods, and that with the exhaustion of our better ores we will be compelled to seek a part of our supply abroad. A partial list of iron ores, with incomplete analyses (Table I), is added, to give a better understanding of the general situation and explain to some extent the reason for things being as they are in the iron and steel trade of the world and to help in bringing this paper to an informing conclusion. The question of the world supply of iron ores has been a subject for study on the part of geologists and engineers for many years, and found its best results in the Eleventh International Geological Congress, appropriately held at Stockholm, Sweden, in 1910. The proceedings are published in two volumes and are undoubtedly the best records available on this subject at the date of publication. It should be borne in mind, however, that much has happened in the 20 years since these figures were assembled. There is just as much known ore at present as at that time, minus the quantity consumed, plus newly discovered reserves. The World War had great effect upon this situation; during that time explorations were greatly reduced and the settlements after the

Jan 1, 1929

By Akira Yazawa, Alžbeta Gubcova

RECENT lead-smelting techniques have tended toward use of high-grade concentrates with minimum amounts of flu, accompanied by profitable employment of roast reaction.1-5 In order to better understand these smelting processes, thermodynamical calculations have been carried out on the Pb-S-0 system, and the results obtained have been presented in isothermal reaction diagrams in which log Ps, and logPo, were the axes. The diagram thus constructed seems to be more convenient to grasp the equilibrium aspect than those published hitherto.6-8

Jan 1, 1968

By Ivan E. Goodner, Charles H. Fulton

THE subject of the constitution of copper-iron mattes has received considerable attention in recent years by Keller,1 Bolles,2 Hofman,3 and Gibb and Philp.4 Still more recently Friedrich, Röntgen, Wiedmann, Heyn and Bauer, and Leroux have published, in some instances, elaborate researches on the various systems of the sulphides, and the sulphides and their respective metals, which enter into the constitution of mattes, and have added very greatly to the knowledge of the subject. The work of Friedrich has been especially fruitful. But to date no effort has been made to correlate the data obtained in the latter researches and apply then to the study of the product called " matte," which is made in such large quantities by copper and lead-smelters. In this paper we propose to determine, by metallographic and chemical means, the constitution of copper-iron and copper-lead mattes in the light of the recent data above mentioned. We do not discuss copper-nickel mattes or speisses (artificial arsenides). The paper is divided into three sections I. A review and discussion of the various binary systems of the metallic, sulphides, and the binary systems of various metals and their respective sulphides entering into the constitution of mattes; also a discussion of the physical and chemical properties of these sulphides. II. A description of the results obtained from the chemical and metallographic examinations of the samples of copper-iron and copper-lead-iron matte obtained from various plants.

Nov 1, 1908

By B. Wilshire, P. W. Davis

It has been shown that grain-boundary migration during high-temperature creep can reduce or even prevent the formation of intercrystalline voids, giving a considerable increase in ductility.' A similar observation has been made in a recent investigation of the creep properties of various grades of nickel and nickel alloys. The results can be illustrated by the observations made on: a) Pure vacuum-cast nickel (99.993 pct Ni) b) Impure vacuum-cast nickel (99.97 pct Ni) c) Pure nickel containing internal voids (produced by a process of intering). d) A substitutional solid solution alloy of pure nickel containing 1.16 pct Sn. All the materials were given a high-temperature anneal (>850°C) to produce a stable grain size of 7 to 10 grains per linear mm. The apparatus and techniques used to obtain the present results have been described elsewhere.' In this series, grain growth was observed only in the highest-purity, vacuum-cast metal. Thus we may consider that in the other materials grain-boundary migration was prevented by either preexisting voids or solute atoms. The effect of migration on the creep ductility of the above materials can be seen from Fig. 1, which

Jan 1, 1962

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By Charles Jones

IN the winter of 1902, while occupying the position of mining and examining engineer for the Mountain Copper Co., Ltd., of Keswick, Cal., I had occasion to discuss with the General Manager, among other things, the question of the enormous waste of sulphur in smelting cupriferous, pyrite ore, and to cast about for means to utilize this waste or to render the fumes innocuous to vegetation. The decreasing rate of production of California farms, the consequent need of fertilizers, and the opportunity thus offered to utilize large quantities of sulphuric acid in the manufacture of superphosphates naturally brought the subject to the practical and commercial side of phosphates. I was informed that the company had made efforts to find phosphates in the West, without success. I advised as a start placing inquiries for phosphate deposits on the Pacific coast in the current mining ,journals. This was done, with the result that in January, 1903, from an advertisement in the Mining and Scientific Press we got track of a deposit in Rich county, Utah, through T.J . Wilson, of the Southern Pacific railroad in San Francisco. As soon as snow in the mountains would permit, in May, 1903, I undertook an examination of the property, with the result of recognizing the importance of the find, in spite of its lack of facilities for transportation at a commercial figure. On June 15, 1903, I concluded my report by saying, "This may be one of the world's deposits of phosphates." On Nov. 17, 1903, I concluded my report for the season in the following words : " I have now no hesitation in saying that I believe the Carboniferous formation so largely developed in the Wasatch mountains of Utah and the mountains of the Great Basin will prove to be one of the greatest storehouses of phosphoric acid in the world."

Jan 10, 1913

By O. U. Bradley

THE extent of losses, due to evaporation, sediment, and water, in crude oil stored in steel tanks, is a very interesting question, and particularly so at this time, when every reasonable measure should be employed to eliminate all possible losses of this important natural product. Available information on this subject is incomplete; e.g., during the development of the Cushing Field, considerable surplus oil was stored in steel tanks, but from time to time, owing to changes in weather, somelosses by evaporation and short storage room on the leases, these tanks were topped out, thus rendering inaccurate any system designed to determine the average rate of evaporation or other losses of the oil over a given period. , Furthermore, the losses, as shown by the records at the time, as a result of hasty gages, failed to take into account the temperature and gravity of the oil. Losses may be classified roughly as occurring from evaporation, presence of sediment and water, and leakage. The coefficient of expansion and contraction of crude oil, in relation to temperature conditions, is of material importance; also, the rate of evaporation is dependent upon the gravity of the oil, as the escape of the lighter hydrocarbons in fresh Cushing oil, of from 40 to 42 gravity, on a warm day is considerable, and from available records of temporary storage, it is safe to assume that a loss of 1 to 13 per cent. in volume will easily occur in light crude oil of Cushing grade over a period of. 6 months, including the summer season. The presence of sediment, water, and other impurities, in the oil will also cause, more or less deterioration in quality, particularly when the fresh production is run direct from the. gage tanks, or from the wells on the lease to steel storage, as is often the case when an oil field is being rapidly developed. The bad oil will settle to the bottom of the tanks and may be determined by thiefing and running a centrifuge test on the sample. The amount of water in the oil depends entirely on the conditions under which it is produced. Sometimes in large producing wells, with heavy gas pressure, some water may come in with the oil, particularly if the well has been drilled to the top of a water sand. Under these conditions, cut oil is often produced, which, if not settled out, is carried over into the steel tanks.

Jan 7, 1918

By Eugene R. Rice

There are many methods for determining the meridian, but all of those in common use involve at least two separate observations, one for latitude and one for azimuth. Such observations made upon a south star at any hour are open to the objection of possible inaccuracy due to ignorance of the absolute refraction, and also to slow change in the altitude of the star when near the meridian. The method of observing a circum-polar star at elongation. besides requiring a separate observation for latitude, is open to the serious objection that clouds may obscure the star at the critical moment. Moreover, a tedious wait for the star to come to elongation is sometimes necessary. Many of us can recall 'long, cold, weary vigils, waiting for Polaris to reach elongation. For observing a circumpolar star at any hour, not only the latitude, but also the true time, must be known. This it is practically impossible to obtain, except in regions reached by the telegraph, and usually then one has to know the longitude also, in order to reduce " standard time" to " local time." The results obtained by this method, when the star is at culmination, are not very good, unless the true local time is absolutely known. The methods of obtaining the nleridian from the sun, by means of a solar attachment, or by direct observation, while good, are not absolute, by reason of refraction, change in declination of the sun, and small change in vertical angle, when the sun is near the meridian. For these two methods, latitude, time, and approximate longitude have to be known. In the method here described, only one observation is needed, and from it are computed azimuth, latitude, aud sidereal time. In other words, one call observe a circumpolar star—Polaris

Jan 1, 1911

By A. C. Fieldner, W. A. Selvig

For purposes of coal classification it is desirable to know the composition and calorific value of the pure coal substance; that is, of the coal free from its ash-forming minerals. Two methods suggest themselves: (1) To free the coal from most of the ash-forming material previous to the analysis; and (2) to analyze the coal as received and calculate the analysis, with certain more or less arbitrary corrections, to the pure-coal basis. Calculation methods are obviously more apt to give correct results with low-ash than high-ash coals. With coals of unusually high ash it would appear preferable to remove, previous to the analysis, as much of the inorganic matter as possible, by float-and-sink or acid-treating methods. Effect of Ignition on Inorganic Constituents of Coal The need of corrections in calculating analysis to the pure-coal basis is due to the fact that the ash, as determined by ignition, is not the same, in either weight or composition, as the inorganic mineral matter in the coal. On ignition a number of changes occur in the coal such as loss of water of hydration of the shaly material, conversion of pyrite (FeS2) to ferric oxide (Fe203) with evolution of the sulfur as sulfur dioxide or possible fixation of more or less of the sulfur in the ash as calcium sulfate (CaSO4), and decomposition of calcite (CaC03) to calcium oxide (CaO). The amount of sulfur from pyrite which remains in the ash as calcium sulfate depends on the amount of calcite and pyrite in the coal. Certain coals high in both calcite and pyrite show relatively large amounts of sulfate sulfur in the coal ash. The determination of total carbon and hydrogen in coal includes, besides the organic carbon and hydrogen, the carbon of inorganic carbonates such as calcite, and the hydrogen of the water of composition of some of the ash-forming minerals. For detailed discussion of corrections proposed for calculations of coal analyses to the " pure "

Jan 1, 1930

By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By C. J. Beevers

Tlze influence of zirconium hydride precipitate mprphology on the fructure of Zr-H alloys tested at strain rates of 10- sec at 20° and - 196°C and at strain rates of -500 sec.-1 at 20°C has been inves-tigated. The critical stage in the embrittlement of these alloys was the fracture of the zirconium hyhide precipitates to form large interval cracks at a stress of 25,000 10 137,000 psi. In specimens con-temping up to 100 ppm H the preciptates existed as isolafed platelets in the zirconium matrix and their fracture as enhanced by low temperature (—196°C) and high strain rate (-500 set-f) loading. These resl~lts lead to the conclusion that the rate of strain hardening of the zirconium metal controls the frac-tzrm of the hydride platelets. Increased hydrogen contents of 500 to 2000 ppm resulted in an increase in the 1)volume fraction and size of precipitates and crlso led to crack propogation in the hydride at both 20 and —196C at the low strain rates (10'* sec-'). Quenching led to refinerment of hydride precipitate size and reduced the degree of embrittlement at — 196°C; this effect is attributed to the absence of fracture of the fine precipitates. The formation of zirconium hydride precipitates has been shown to be the cause of hydrogen embrittlement of zirconium.' Several investigators'-" have studied the problem in broad outline, demonstrating that impact-loading conditions, testing temperatures below room temperature, and increasing hydrogen content produce increased brittleness. For example, Muehlenkamp and schwope2 showed that the transition temperature for notched impact tests was raised from 150" to 350°C on increasing the hydrogen content from 45 to 490 ppm. The degree of embrittlement is also controlled by the morphology of the zirconium hydride precipitates. The solubility of hydrogen in zirconium decreases from 600 ppm at 550°C to 10 ppm at 20"C,~ so that the form of the zirconium hydride precipitates (ZrH2) can be modified by varying the cooling rate through the Zr-aZr + ZrH2 phase boundary.= Forscher showed that quenching a specimen containing 35 ppm H from above 315°C resulted in a reduction in area of 70 pct at -196"C, whereas slowly cooling from above 315°C resulted in a ductility of half this value. The role of the hydride precipitate in the fracture process has been examined by Young and schwartz6 and more recently by westlake.' From metallo-graphic observations on slowly cooled Zr-H alloys they have suggested that cracks are nucleated in the hydride precipitates by the interactions of twins in the zirconium metal with the hydride. The experiments reported in this paper show that crack propagation in the zirconium hydride precipitates is the critical stage in the embrittlement of Zr-H alloys. The factors influencing fracture of the hydride precipitates and crack propagation in the zirconium metal will be related to the problem of embrittlement. EXPERIMENTAL TECHNIQUES The zirconium used in these experiments was produced from an ingot of vacuum arc-melted iodide zirconium forged down to 1 in. diameter at 800' to 850°C. The 1-in.-diameter bar was surface-machined and cold-swaged to 0.375 in. diameter. After a vacuum anneal at 800°C for 1 hr the hardness was 60 to 70 Vdh. The total impurity content was approxi-

Jan 1, 1965

By Thomas Leonard Watson

Jan 1, 1906