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By L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,' have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson' have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive

By Thomas R. Smith

This paper covers oil shale resources in those countries that border the Pacific Rim. The major known resources around the Pacific Rim occur in the Western United States, Australia, the People's Republic of China, (PRC) and the Thailand/Burma region. The location of these deposits is shown in Figure 1. In 1965, the U.S. Geological Survey estimated world oil shale deposits of over 4 quadrillion tons having a potential oil yield of over 2 quadrillion barrels. If all this were extracted, it could meet the world's entire energy needs far into the future. However, the Survey also estimated the spent shale waste could cover all of the surface of the world to a depth of about 10 feet. Thus, for this and many other technical and economic reasons, it does not appear to be feasible to develop a large portion of the world's oil shale resources in this century; nor will shale in itself solve our energy problems. Nevertheless, shale oil and other ' synthetic fuels are expected to play an important role in new energy supplies in the longer term. WHAT IS OIL SHALE OR SHALE OIL? The term "oil shale" is sometimes a misnomer, in that the rock is often more of a limestone or siltstone than a shale. The common link between resources termed “oil shale" is that they all contain an insoluble substance cal led kerogen (which is from the Greek words for waxmaking). Kerogen is a form of organic carbon derived from a variety of plants ranging from algae to higher plants. When heated sufficiently, the kerogen generates hydrocarbons called shale oil, a form of synthetic crude oil that in most cases is lower in hydrogen content than conventional crude oil. The amount of oil in oil shale is relatively small --roughly 10 percent (by weight) in the richer shales. To upgrade this synthetic oil to usable products, additional processing is necessary. This brief sketch gives an idea of what this different, but significant, form of hydrocarbon is like. ENVIRONMENTS OF DEPOSITION Most oil shale deposits fall into three environments of sediment deposition: 1ake (called lacustrine), sea (marine) and river (fluvial-deltaic). In each case, the deposition of oil shales took place in quiet water environments where plant life, particularly algal plants, could flourish and, after dying, be deposited in unoxygenated water where the kerogen precursors would be safe from destruction by oxidation. The oil shales that were deposited in large lake basins (lacustrine) have attracted the most attention for development over the years. They often have multiple seams, deposited in a cyclic nature with extensive areal distribution and rapid vertical changes in kerogen content. Grades are moderate to high, ranging from 80 to 200 liters per tonne. Rundle in Australia and the Piceance Creek Basin in Colorado are examples of this type. Both deposits represent large volumes of oil shale in small areas which could provide the large volume of feedstock needed for future commercial operations. The stratigraphic sections of these two deposits feature thick oil shale seams with average grades of 80 - 125 liters/tonne conducive to both open pit, and underground operations. However, the rock strength of the Rundle shale is not sufficient to - support underground mining. On the other hand, the Colorado deposits, being more carbonate in nature, are sufficiently strong to support either type of mining depending on the overburden to ore ratio. These latter types of deposits will likely provide the first target for development of a commercial industry. The marine type is characterized by extensive areal distribution with relatively thin seams. The grades are generally low to moderate, ranging from 50 to 120 liters per tonne. The marine oil shales are common worldwide, and their attractiveness for mining is dependent on the overburden to ore ratio. Because of their widespread areal distribution, their in situ resources can be quite large. The Toolebuc Formation in Central , Queensland, Australia is a good example of this type of deposit being 7-10 meters thick over an extensive area. The Julia Creek deposit with its favorable overburden-to-ore ratio is being studied for possible development. In a fluvial-deltaic environment, there are many small lakes or bogs associated with rivers in which a very pure type of oil shale called torbanite could form. Torbanites are very high grade containing up to 75 percent hydrocarbons. The known occurrences are generally small lenticular deposits associated with coal seams. Even with the high grades, it is not likely that any of the known deposits would warrant commercial development because of their small size. The torbanite deposits in New South Wales, Australia were processed prior to World War I1 near the town of Glen Davis. However, today's known resources of this type are not large enough to warrant a commercial plant.

Jan 1, 1982

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By Stanley L. Lopata, Eric B. Kula

SEVERAL methods are available for determining pole figures by X-ray means.' The earlier film methods have been replaced by techniques in which the intensities are measured by Geiger counters on an X-ray diffractometerZm7. These methods utilize either flat transmission or reflection samples,214°8 cylindrical specimens,3 or spherical specimens.7 A single transmission or reflection sample will not yield information over the complete pole figure. The cylindrical specimens suggested by Nortod and the spherical specimen of Jetter and Borie7 have the advantage of allowing the whole pole figure to be obtained without any corrections to the intensity for absorption, There is a lower limit to the size of sheet which can be conveniently studied, however, and sample preparation can be rather tedious. Probably the most common method today for determining the complete pole figure is that developed by Schulz. A flat reflection sample is used for determining the pole figure from the center out to about 70". Because of the geometry of the system used, little or no correction for absorption or irradiated volume is necessary.4'6 A separate transmission sample is used for the region near the edge of the pole figure. This procedure requires two separate samples, one of which must be a thin carefully-prepared transmission sample. Furthermore, since the reflection and transmission data are in different arbitrary intensity units, a region of overlap must be obtained, and the intensity data from one set of measurements converted to units of the other. These are serious disadvantages of this method, and they point out the need for a simplified procedure. Since the reflection technique can be used for planes whose normals lie up to about 70° from the sample surface normal, it is apparent that a complete pole figure can be obtained by reflection alone if sample surfaces are cut at oblique angles to the rolling plane Specifically, if a rolled sample is cut so that the normal to the surface formed lies equidistant (54" 44') from the rolling plane normal, rolling direction, and transverse direction, then complete information for one quadrant of the pole figure can be obtained by reflection from the surface. Fig. 1 shows this oblique surface, as well as the position of the pole of this surface in the pole figure. When a surface has been cut oblique to the rolling plane, the standard polar stereographic net is inconvenient to use, and it would be more desirable to have the center of the net coincide with the pole of the oblique plane. Fig. 2 shows such a net, where the center has been offset 54' 44' to correspond to a specimen cut as in Fig. 1. This net was in effect obtained by rotating a standard polar stereographic net 54" 44' with the help of a Wulff net. With the experimental setup used. a sample can be cut from plate of 1/2-in. thickness or br Gen- erally thinner sheet is under investigation, and a composite specimen must be used. A convenient procedure has been to bond together, using epoxy resin, sufficient sheets to form a cube. These are clamped in a vise, and when dry, the whole vise is rotated and a flat surface ground at the required angle. The sample is then mounted inside a larger steel ring using Koldmount, the backside ground flat and parallel to the approximate desired thickness. The sample is then polished and etched to remove any effects of cold working during grinding. With this method only one quadrant of the pole figure is obtained. Often pole figures show symmetry around the rolling and transverse directions, and any slight asymmetry is due to scatter. Should the pole figure not be symmetrical, four oblique surfaces, corresponding to the four quadrants of the pole figure, would have to be examined. In most cases there is symmetry at least around the rolling direction, which reduces to two the number of quadrants to be investigated. For many purposes all that is required is an average polefigure for the four quadrants. This canreadilybe obtained with composite specimens of sheet material, where sheets Corresponding to each of the four quadrants can be intermixed. The four quadrants can be obtained by considering sheet in the normal position, and by rotatiolls of 180" around the sheet normal, the rolling direction, and the transverse direction. If desired, the whole thickness of the sheet can be used, yielding an average of the surface and interior textures; or the surface material can be removed from each sheet, resulting in a pole figure for the center alone. Eugene S. Meieran of the Massachusetts Institute of Technology has independently developed the same method. His results, adapted to a pole figure goniometer with a specimen spiraler, will be described in another publication.

Jan 1, 1962

By D. M. McFarland

A FEW years ago a novel electric detonator known as the split-second or millisecond delay electric blasting cap was introduced for use in quarry blasting. Regular electric blasting caps fired in series may be depended upon to fire within a millisecond or so from the first to the last in a series. Regular delay electric blasting caps are provided that fire one period after the other period in intervals of 1/2 to possibly 11/2 sec. Most split-second or millisecond delays are designed to fire one period after the other period in possibly 25 to 50 millisecond intervals. The ear is not capable of detecting time intervals of this magnitude. The primary thought at the time millisecond delays were introduced was to investigate the results on rock breakage by firing a line of holes in a quarry face so that charges in adjacent holes would not be detonated simultaneously. This could not be accomplished satisfactorily with regular delays. The time interval between successive periods of 1/2 to 1 sec was sufficient to permit considerable movement of the burden. If the burden of one hole was reduced to a great extent by the firing of an adjacent hole, the firing of the hole with the reduced burden would likely reveal this lack of confinement by a terrific report and wild throw of rock. In the early blasts with millisecond delays it was observed that instead of the usual sharp report, the blast had a muffled sound and vibration was not as perceptible as when simultaneous firing was used. Because many quarry operators were being threatened with injunctions or suits for damages by neighbors who claimed structural damage to their buildings, millisecond delays were tried extensively in quarries. In the majority of these trials, the results were very satisfactory. The seismologists recorded the ground movement created by many blasts and verified the initial observations that millisecond delays could be used to reduce vibrations appreciably. In the past few years the advantages of this principle of nonsimultaneous firing of the charges in blasts has become generally accepted. Today the quarry operator who has vibration troubles, inadequate breakage, and excessive backbreak and has not investigated the possibilities of millisecond delay blasting is ignoring a remedy that has proved satisfactory for many. His complacency may be costing him money. Because of the results attained in quarry blasting, it was logical that millisecond delays should be tried in construction work such as in road cuts. As formations in this type of work are likely to change rapidly with advance of the cut, it is more difficult to evaluate results than in quarry blasting. However, this improved control over timing has been beneficial in limiting throw, promoting fragmentation, and reducing overbreak. In blasting near buildings the reduction in vibration and in throw has been especially helpful. As blasters employed in construction work learn what may be accomplished by closer control over the time of firing of explosives charges, more and more millisecond delays are being used to supplant instantaneous electric blasting caps. Improved Fragmentation Underground With this background of promising results, it was not surprising that millisecond delays should go underground. In limestone mining use of millisecond delays as compared with use of cap and fuse or electric blasting caps showed improved fragmentation in stopes and in slabbing operations. Then an opportunity developed to use millisecond delays in some tunnels being driven in a limestone mine (fig. 1). Using the normal charge employed and merely substituting three millisecond delay periods for three regular delay periods, there was a noticeable difference in the appearance and the position of the pile of rock after a blast. A greater portion of the face was exposed, the crest of the pile was farther from the face, and the pile was heaped high along the center line of the tunnel leaving room to walk along the ribs to the face. Fragmentation was appreciably increased. It gave the impression that the slabs had been thrown against each other with tremendous force, promoting the movement of the broken rock along the center line of the tunnel away from the face. Because the drilling and the charge weights were unchanged, the evidence was convincing that the difference in timing was responsible for the difference in results. Probably a greater portion of the energy from the explosives had been expended in doing useful work on the rock. Zeros followed by two periods of millisecond delays were used in the V cut and in two slabs to either side of the cut in this simple round. When millisecond delays, substituted period for period for regular delays, are first tried in a drift round in a mine, and the usual charge of explosives

Jan 1, 1951

By D. M. McFarland

A FEW years ago a novel electric detonator known as the split-second or millisecond delay electric blasting cap was introduced for use in quarry blasting. Regular electric blasting caps fired in series may be depended upon to fire within a millisecond or so from the first to the last in a series. Regular delay electric blasting caps are provided that fire one period after the other period in intervals of 1/2 to possibly 11/2 sec. Most split-second or millisecond delays are designed to fire one period after the other period in possibly 25 to 50 millisecond intervals. The ear is not capable of detecting time intervals of this magnitude. The primary thought at the time millisecond delays were introduced was to investigate the results on rock breakage by firing a line of holes in a quarry face so that charges in adjacent holes would not be detonated simultaneously. This could not be accomplished satisfactorily with regular delays. The time interval between successive periods of 1/2 to 1 sec was sufficient to permit considerable movement of the burden. If the burden of one hole was reduced to a great extent by the firing of an adjacent hole, the firing of the hole with the reduced burden would likely reveal this lack of confinement by a terrific report and wild throw of rock. In the early blasts with millisecond delays it was observed that instead of the usual sharp report, the blast had a muffled sound and vibration was not as perceptible as when simultaneous firing was used. Because many quarry operators were being threatened with injunctions or suits for damages by neighbors who claimed structural damage to their buildings, millisecond delays were tried extensively in quarries. In the majority of these trials, the results were very satisfactory. The seismologists recorded the ground movement created by many blasts and verified the initial observations that millisecond delays could be used to reduce vibrations appreciably. In the past few years the advantages of this principle of nonsimultaneous firing of the charges in blasts has become generally accepted. Today the quarry operator who has vibration troubles, inadequate breakage, and excessive backbreak and has not investigated the possibilities of millisecond delay blasting is ignoring a remedy that has proved satisfactory for many. His complacency may be costing him money. Because of the results attained in quarry blasting, it was logical that millisecond delays should be tried in construction work such as in road cuts. As formations in this type of work are likely to change rapidly with advance of the cut, it is more difficult to evaluate results than in quarry blasting. However, this improved control over timing has been beneficial in limiting throw, promoting fragmentation, and reducing overbreak. In blasting near buildings the reduction in vibration and in throw has been especially helpful. As blasters employed in construction work learn what may be accomplished by closer control over the time of firing of explosives charges, more and more millisecond delays are being used to supplant instantaneous electric blasting caps. Improved Fragmentation Underground With this background of promising results, it was not surprising that millisecond delays should go underground. In limestone mining use of millisecond delays as compared with use of cap and fuse or electric blasting caps showed improved fragmentation in stopes and in slabbing operations. Then an opportunity developed to use millisecond delays in some tunnels being driven in a limestone mine (fig. 1). Using the normal charge employed and merely substituting three millisecond delay periods for three regular delay periods, there was a noticeable difference in the appearance and the position of the pile of rock after a blast. A greater portion of the face was exposed, the crest of the pile was farther from the face, and the pile was heaped high along the center line of the tunnel leaving room to walk along the ribs to the face. Fragmentation was appreciably increased. It gave the impression that the slabs had been thrown against each other with tremendous force, promoting the movement of the broken rock along the center line of the tunnel away from the face. Because the drilling and the charge weights were unchanged, the evidence was convincing that the difference in timing was responsible for the difference in results. Probably a greater portion of the energy from the explosives had been expended in doing useful work on the rock. Zeros followed by two periods of millisecond delays were used in the V cut and in two slabs to either side of the cut in this simple round. When millisecond delays, substituted period for period for regular delays, are first tried in a drift round in a mine, and the usual charge of explosives

Jan 1, 1951

By R. Bakish

A. B. MICHAEL and F. J. Huegel1 recently re- ported on dislocation configurations in are-cast columbium. This communication discusses observations made in our laboratory on etch structures believed to be associated with dislocations

Jan 1, 1959

On June 1, the offices of the Engineering Division of the National Research Council were moved from Washington to the sixteenth floor of the Engineering Societies Building, 29 W. 39th St., New York City.

Jan 7, 1919

Vol. 54 will be sent about February 1 to members who have paid their dues for the current year. Members who do not receive copies within a reasonable time are asked to notify the Secretary.

Jan 2, 1917

By A. S. Learoyd

THE Anthracite Division, Bureau of Distribution, of the United States Fuel Administration, came into existence about Oct. 20, 1917. There had been no definite policy determined upon and the distribution had been carried out by the producers and distributors of this fuel as under normal conditions. The domestic sizes had been shipped from the beginning of the coal year on Apr. 1 in about their usual proportions to the various sections of the anthracite consuming territory of this country, which, in a general way, extended as far west as Nebraska and Montana, and in the south along the Atlantic seaboard to Florida. With the advent of cold weather, about the middle of November, acute shortages commenced to develop all over the northeastern section of the country, due to largely increased demand by the public in general, to enormously increased population in centers where industrial war activity was concentrated, and by the needs of the war industries themselves. Commencing with the early part of December, this demand was aggravated by extreme low temperatures and heavy snow; and the production decreased for the same reasons. From that date until the change in the weather, about the latter part of February, it was simply a question of getting coal into communities as emergencies occurred, to take care of individual cases. No definite plan of distribution could be followed. The coal mined between Apr. 1 and Nov. 1 had been distributed as mined and, therefore, only current production was available for distribution. The Anthracite Division, during this period, consisted of a Director, two assistants, together with an office force of seven or eight clerks and stenographers.

Jan 8, 1919

By J. Blodget Britton

SIX different samples of anthracite, each a firm compact lump, were finely pulverized and immediately put in bottles. Portions of these were weighed and placed upon an ordinary water-bath and dried for one hour; the average loss was 1.24. The same portions were then placed in a hot-air oven, and for two hours kept at a temperature of 285' F., and, after cooling in a dry chamber, were again weighed, when there was found a further average loss of 1.22, making a total so far of 2.46. They were then immediately returned to the oven and for two hours more kept at a temperature of 530' F. and cooled and weighed again, when no further loss was found, but an average gain of .55 upon the previous weighing. The same portions were a third time placed in the oven and for about ten minutes kept at the last-mentioned temperature, and then, while still hot, were poured into one-quarter inch glass tubes, each with a bulb at one end, and heated over a Bunsen burner at a temperature below a red heat, when more water vaporized and condensed in small clear globules on the cold parts of the tubes. Fresh portions of the coals were then taken, and the total amount of water determined, and the average was found to be 3.04, or 1.80 more than was found at the temperature of the water-bath, which was perhaps a little below 212' F., and .58 more than at 285' F. Tests were afterwards made by placing other fresh portions of the

By E. J. Schmitz

This section was obtained last year during an examination of the iron-ore resources of the Rich Patch Mountain region and along Craig's creek valley. The geological members below the Oriskany and Lower Helderberg are exposed along the gap in a beautiful arch, while the higher formations appear in a more or less disturbed state on both sides of this arch, and are partly covered by dèbris. I have thought it of interest to the Institute to reproduce the drawing of this section at the gap which I made in my note-book at the time of my examination; those parts of the section, which lie at both sides of the arch, are only approximated. I give also a number of notes and measurements, referring to the Clinton formation and especially to the characteristics of the fossiliferous ore-seam opened in the various tunnels along the arch (see section). I. In Tunnel C: For the first 110 to 120 feet to second shute, we find the ore only here and there in small deposits, and interchanging with, or changing into, either a very siliceous limestone or a sandstone. About 10 feet beyond shute we have : Sandstone roof. Clay-slate, 211/2 inches Brown lean ore, 1 inch. Sandy clay, 3 to 31/4 inches. 1. Dark .brown ore, 3 inches. 2. Fossil-ore, changing into sandstone or very siliceous limestone, 2 inches. 3. Brown lean ore, 6 inches. Clay and slate below, 1 foot. 194 feet from entrance : Sandstone roof. Clay-slate, 4 inches. Clay 15 inches. Fossil-ore, 63 to 7 inches. Clay and ore, If inches. Lean brown ore, 2 inchea. Clay to bottom, 2 feet.

Jan 1, 1896

By J. Blodget Britton

Six different samples of anthracite, each a firm compact lump, were finely pulverized and immediately put in bottles. Portions of these were weighed and placed upon an ordinary water-bath and dried for one hour; the average loss was 1.24. The same portions were then placed in a hot-air oven, and for two hours kept at a temperature of 285° F., and, after cooling in a dry chamber, were again weighed, when there was found a further average loss of 1.22, making a total so far of 2.46. They were then immediately returned to the oven and for two hours more kept at a temperature of 530° F. and cooled and weighed again, when no further loss was found, but an average gain of .55 upon the previous weighing. The same portions were a third time placed in the oven and for about ten minutes kept at the last-mentioned temperature, and then, while still hot, were poured into one-quarter inch glass tubes, each with a bulb at one end, and heated over a Bunsen burner at a temperature below a red heat, when more water vaporized and condensed in small clear globules on the cold parts of the tubes. Fresh portions of the coals were then taken, and the total amount of water determined, and the average was found to be 3.04, or 1.80 more than was found at the temperature of the water-bath, which was perhaps a little below 212° F., and .58 more than at 285° F. Tests were afterwards made by placing other fresh portions of the

Jan 1, 1877

By H. J. French

AT THE request of a committee of the Engineering Division,1 National Research Council, a study of the properties of boiler plate at various temperatures up to about 900° F. (482° C.) has been instigated. The following is a report of preliminary tests made on two grades of ½ -in. plate and includes a description of the apparatus used in the determination of the proportional limit. Detailed reference to the many published investigations in connection with the properties of steel at various temperatures will be omitted from this report. Suffice to state that results obtained for variation in tensile strength elongation, and reduction in area with temperature are in substantial agreement with the effects now generally considered to be correct. Comparison of proportional limit values with results obtained by other investigators will be found in the conclusions.

Jan 2, 1920

Frank 11. Probert, Neudorf, Anhalt, Germany (communication to the Secretary): I have read with much pleasure Mr. Collier's valuable paper. But the system of timbering which he describes as used in the levels, stopes, etc., though it must be admitted to be very strong and safe, seems to me somewhat extravagant. The amount of timber required every month for such a system must be enormous; and only where suitable material could be cheaply obtained would such a plan be economically practicable. The first point which strikes me is the unusually great diameter of the timber employed. In the mines of Pfaffenberg and Meiseberg, which are under my supervision, the country-rock consists of argillaceous slates, traversed by innumerable small fissures or joints, dipping at all angles and striking to all points of the compass. Undoubtedly, this net-work has been caused by the upheaval of granite masses in the vicinity. Each fissure is accompanied by a more or less well-c1efinc.d gouge or fluccan, caused by the rubbing together of the slates at or after the original disturbance. In such

Jan 1, 1900

By T. S. Fuller

MUCH study has been given by engineers in general, and investigators in particular, to the concentration of stress which occurs under load in structural members having irregularities in section such as notches, shoulders, key ways, tool marks, etc. The result of the effect of both fresh and salt water corrosion upon the endurance properties of various metals and alloys has been ably determined and the general laws underlying these phenomena carefully pointed out by McAdam. From a practical standpoint, 'however, it is after all the endurance value of corroded, non-symmetrical sections which is most pertinent. In the experiments about to be described rotating cantilever specimens of nickel steel of the 3.5 per cent nickel ' 0.35 per cent carbon type have been used. These were machined from bars l 1/8. in. dia. and 9% in. long and were heat-treated by quenching in oil from 825 deg. C. followed by reheating to 650' C. and oil quenching. The tensile and impact properties of this material so heat- treated follow:

Jan 1, 1931

Discussion of the paper of E.. C. LEE, presented at the St. Louis meeting, October, 1917, and printed in Bulletin-No. 130, October, 1917, pp. 1825 to 1832. H. M. WILSON, Pittsburgh, Pa.-The statement ill the paper of T. T. Read, "Increasing Dividends Through Personnel Work;" that the offering of substantial money rewards for avoidance of accidents is much more effective than mere propaganda or education respecting accident prevention, is a, point fully substantiated in the experience of insurance inspection under workmen's compensation acts. The first year under the Workmen's Compensation Law in Pennsylvania, during which over 2000 mines were tinder the observation and protection of the inspectors of the insurance companies, has resulted in several inspections of each mine, a splendid cooperation .between the operators, the State mine inspectors and the insurance inspectors, and an average reduction in premium rate for insurance from $3.83 to $2.77, a reduction of more than $1 per $100 of payroll, on an average payroll of nearly $100,000,000, In other words, the insurance companies have

Jan 1, 1918

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3', as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965