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By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (Al2Si4O10(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By Walter B. M. Davidson

Phosphorus is one of the elements having the widest distribu tion, and phosphoric acid plays an important part in the composition of the crust of the earth. It is allied in various chemical combina- tions with many bases, of which lime, alumina and iron are the most common. It is difficult to state in what chemical combination phosphoric acid predominates in the crust of the earth, for while phosphate of lime, as the mineral which is sought for and found in deposits of economic value is the most familiar, it is probable that the phosphates of alumina and iron are the most usual forms in which phosphoric acid exists in all soils not essentially calcareous. It has been shown by thousands of analyses that all fertile soils contain from a trace to 0.5 per cent. of phosphoric acid. All limestones, dolomites and chalks contain it in proportions which, though usually small, are large enough to make careful analysis necessary in the selection of limestone as flux for iron-smelting. It is generally Trenton limestones that are found best for this purpose, the more recent strata being more phosphatic. In some places phosphoric acid replaces carbonic acid, and the limestone or chalk becomes phos phatic to a large degree, or sometimes pure phosphate of lime. The waters of the ocean, from very early periods, have contained phosphoric acid. Different analyses show varying contents; it is asserted that some portions of the Gulf Stream are more phos phatic than the surrounding waters of the Atlantic. Many springs, usually from limestone regions, contain soluble phosphates in vary ing quantities. I think it safe to assert that phosphorus is nearly the most widely and evenly distributed element on the surface of the earth, and probably the most subdivided. This can be readily understood when the important part which phosphoric acid plays and has played in the vital cosmos is taken into consideration. Phosphorus was on the earth in gaseous, liquid or solid form before the dawn of life, and since then all animal and vegetable creation have combined with the

Jan 1, 1893

By Eugene McAuliffe

THE Coal Division undertook its most ambitious program this year at the New York meeting, with six full' sessions and a luncheon on Monday which had a record attendance and at which the newly elected officers for the Division were announced. Eugene McAuliffe, president of the Union Pacific Coal Co., Omaha, Neb., was unanimously selected as Chairman; J. B. Morrow, preparation manager of the Pittsburgh Coal Co., as Vice-Chairman; and H. E. Nold, Ohio State University, Secretary. During the past year two new and interesting activities were conducted by the Division directed at stimulating the interest of junior and student members. Reports were presented at the luncheon meeting by the chairmen of these commit¬tees. J. B. Morrow. chairman of the paper prize awards, and H. N. Eavenson reported on the work of the mining machinery manufacturers fellowship, the work on which was completed the first of the year. Several excellent papers are expected from these two groups for the next meeting of the Division to be held in Pittsburgh some time in the fall. The regular six-session program was filled from start to finish with interesting papers and much discussion, but unfortunately not enough time for the latter. The papers covered the field of prospecting, mining methods, preparation, utilization, mechanization, and safety, and all through the program we were constantly reminded of the value and need of research in the coal industry.

Jan 1, 1936

By R. S. French

THE purpose of this paper is to present data that have been obtained during the past two years concerning the effects of prior cold-work and temperature and time of anneal upon the recrystallization and grain growth of 70-30 cartridge brass. It was desirable to study certain of these phases so that an accurate picture of the principles of the subject could be shown. The work is not intended to provide explicit annealing data, but to provide material examples that may help to clarify analogous problems concerning this alloy. Specifications often set limitations upon the grain size of annealed materials because of the importance of grain size upon subsequent manufacturing operations. It was, therefore, worth while to study the variables that affect the recrystallized grain size of this material. C. H. Mathewson and A. Phillips,1 W. R. Webster,2 and others have presented annealing characteristic curves of this alloy. A recent typical curve presented by R. S. Pratt3 is shown in Fig. I. The tensile properties and grain sizes are shown as functions of the annealing temperature. Such curves serve as a useful guide in determining the physical properties of annealed material, but as they are made generally under carefully controlled laboratory conditions they do not indicate the performance of metal annealed in a mill muffle, where conditions are different and the amounts of metal require necessarily longer heating times and temperatures. Study of the effect of time and temperature upon grain growth and subsequent recrystallization was made with a coil of metal having the following analysis: 70.04 per cent copper; 0.007 lead; 0.007 iron; 0.00 tin; 0.00 silicon; 0.001 nickel; 0.000 phosphorus; balance zinc. The sample coil was obtained from metal that had been rerolled from hot-rolled mill stock, and was received at 0.228-in. gauge, soft, with a grain size of 0.125 mm. This material was then rolled 43.5 per cent to 0.125-in. gauge and annealed to a 0.053-mm. grain size. In this condition, samples were cut and used in all of the experimental work reported in this paper. TIME The first study was of crystal growth at a constant temperature over a moderate length of time. Material was cut from the stock coil at 0.129-in. size and rolled 75 per cent hard to 0.032-in. gauge. From this piece small samples were cut ½ by 2 in., suitable for grain-size determinations. Twelve samples were placed in an electric furnace uniformly across the width, approximately an inch from the floor, A thermocouple was wired to the center sample, so that the approximate metal temperature could be followed. At various

Jan 1, 1944

By Richard E. Chism

SAN DIMAS, in the State of Durango, Mexico, on the frontier of the State of Sinaloa, is the centre of an extensive and rich mining region, which has been exploited for over a hundred years; and the patio process for working silver ores has there attained the highest perfection of which it is capable. Local modifications have been engrafted upon the underlying principles of the process, but, as a whole, the San Dimas practice so fully illustrates its typical capabilities, that I have undertaken to describe its workings in the hope of lightening, to some degree, the labors of my professional brethren who may have occasion to visit Mexico." As is tolerably well known, the patio process, like all other systems of free amalgamation, is not successful with ores containing more than a trace of zinc or lead, the presence of zincblende being especially obnoxious. Iron and copper in small quantities are not particularly disadvantageous. The process succeeds very well with all sulphide ores which do not contain much more than a trace of arsenic and antimony, provided the tailings are concentrated, although, of course, it is best adapted for free milling ores. For suitable silver ores that contain small amounts of free gold the process is still a good one, but where the gold is combined with sulphurets, a considerable and even an excessive loss is inevitable. Hitherto the Mexicans have submitted to this loss, but, since the introduction of American mills, they are gradually abandoning the patio process in favor of the other. The San Dimas ores have a gangue of quartz and feldspar. They are composed principally of silver sulphides, with some chloride and

Jan 1, 1883

By James A. McGurty, Walter J. Koshuba, Samuel G. Gordon, Gilbert E. Klein

ONE of the problems encountered in working with metals at elevated temperatures is the instability resulting from solid-solid diffusion at a -common interface. A determination of the nature and magnitude of this phenomenon is important as related to structural properties of materials potentially useful in high temperature applications. This paper is concerned with the solid state reaction between metallic molybdenum and beryllium at elevated temperatures. In the older literature,' there were no known inter-metallic compounds in the system Be-Mo, and the list of beryllium intermetallics was rather small. New compilations have been made by Smithells' and by Taylor," listing all the then known beryllium binary intermetallic compounds. In addition to these, some new phases have just been reported' in the system Zr-Be and some further compounds of the type MBe,3 have been currently described. The new compound MoBe,, which is reported upon in this paper differs considerably from the above mentioned MBe13 group, and will be discussed in detail. Diffusion Study The nature of the solid diffusion at a Mo-Be interface was determined by sealing a beryllium rod inside a molybdenum capsule and heating at a temperature of 2000°F' (1100°C) for 100 hr. The molybdenum capsule was fabricated from % in. swaged molybdenum rod obtained from the Fansteel Metallurgical Corp. The beryllium metal was obtained from Brush Beryllium Corp. as % in. cold-drawn rod. This material assayed 99.05 pct Be and contained as impurities 0.84 pct Be0 and 0.19 pct Be2C. The molybdenum capsule was % in. in OD x 2 in. long. To prepare it, a concentric hole 0.250 in. + 0.001 in. — 0.000 in. in diam was drilled and reamed in one end of a rod to a depth of 1 '/2 in. A 1 in. long beryllium rod 0.250 in. + 0.000 in. — 0.001 in. in diam was pressed into the molybdenum capsule. A molybdenum plug 0.250 in. & 0.001 in. in diam x 9/16 in. long was then used to seal the beryllium in place. The capsules were placed in a molybdenum resistance furnace and heated at 2000°F (1100°C) for 100 hr. On cooling, the specimens were cut and examined metallographically. Fig. 1 is a micrograph at X250 of a portion of the interface from a transverse section. Four phases are clearly visible, with sharp boundaries between them. Phase A is a section of the molybdenum capsule; phase B is the molybdenum-rich intermetallic composition MoBe,; phase C is the beryllium-rich compound MoBe13; phase D is a section of the beryllium rod. All phases were readily polished to a high metallic luster. The molybdenum-rich phase has a pronounced purple tinge. The beryllium-rich phase (C) is only slightly darker than the pure beryllium. In polarized reflected light, however, it shows striking birefringence between crossed Nicols. The black areas represent flaws or pores in the material. A small representative amount of powdered material from each of the phases was carefully removed under the microscope with a diamond tool. With this material, powder X-ray diffraction patterns were made for the identification of each phase. Table I lists the X-ray diffraction spacings and corresponding indexes characteristic of these intermetallic compounds. Synthesis To establish the formula of the new intermetallic compound, X-ray diffraction patterns were made from powders obtained from solidified melts of known composition. The syntheses were made by

Jan 1, 1952

It is particularly interesting at this time to notice the recommendations of F. L. Bishop, clean of the University of Pittsburgh School of Engineering as to the types of engineers required and the training that should be given each type. Dr. Bishop's recommendations, which follow, are substantially the same as the first two recommendations made by resolution at the National Conference recently held to discuss commercial engineering problems. This provided business training for the engineer arid engineering training for commercial enterprises. Dr. Bishop says: "The first type is that of the man who may be called a technician, who is highly trained in science and mathematics, who possess the instinct of the research man and who can devote his entire time to highly technical research problems, either in the research laboratories which are now rapidly being developed in the large industries, or by applying the results of his research to engineering science. For the training of this type of man, there is needed the best of scientific equipment, the members of the faculty must be those who are intimately interested in research problems, and the student himself must have what is sometimes called a mathematical mind. It is doubtful if this type of nan can be developed in a four-year course under existing conditions. In fact, it is probable that such a man can be developed only M. a school which has a thorough graduate department. "The second type which seems to be demanded by the industries is the man who has a broad general knowledge of engineering subjects and can apply that knowledge in an effective way in present engineering problems. He must have ability to command men, a knowledge of the applications of economic principles to industries, and a broad training in the so-called humanities, since he is the man in contact with men of other types in other fields of human activities. He should not be a research man, his training in mathematics need not be of necessity so extensive as that of the research technician, but his understanding of engineering problems should be extensive. Such a man cannot be trained in the ordinary schools because of the artificial conditions which of necessity exist in academic institutions. He must become familiar with the industries while yet, a student in order that he may understand thoroughly the application of his theoretical courses in school and their application to industries, and also that he may become familiar in the formative period of life with the problems of labor and the human factor in engineering. It is in the development of this type of man, who is to become. the manager and operating head of our large manufacturing industries, that the advantages to be derived from the cooperative system of engineering education are needed."

Jan 9, 1919

By E. C. Pechin

THE Lucy furnace, owned by Messrs. Carnegie, Kloman & Co., and located on the Alleghany River, on the outskirts of Pittsburgh, is a splendid modern furnace, 75 feet high, and 20 feet bosh. She had been working well on low grade ores of about 50 per cent., producing daily 68 to 75 tons. There was on stock 500 tons of Republic ore, one of the purest and best of the Lake Superior ores, averaging over 68 per cent. of iron, which had been procured for the purpose of making a trial for Bessemer iron. This was charged by itself, and Mr. Skelding, the founder, reports that he did not succeed in getting a single cast when it came down, before the furnace chilled from the hearth to the top of the boshes, some 25 feet. Every effort was made to save her, without avail, and the disagree-

Jan 1, 1874

By H. A. Schwartz

FROM time to time, one of the authors has had occasion to investigate the graphitizing reaction and has published the results mainly as discussion1 of the work of other investigators. In view, therefore, of the diversity of both observations and interpretation, it seemed well to attempt a revision of the entire subject in the Research Laboratory of the National Malleable Castings Co. The work consisted of a careful study of a single, impure, iron-carbon alloy. The material, which may be considered typical low-carbon white cast iron of the malleable industry, was an air-furnace iron of the following composition: carbon 2.30 per cent., silicon 1.20 per cent., manganese 0.29 per cent., phosphorus 0.156 per cent., sulfur 0.048 per cent. The freezing range extended from 1213° to 1132° C., the latter figure agreeing with Gontermann's data .2 We have attempted to define the equilibrium diagram of this alloy, in the stable condition as related to the metastable diagram, from a temperature somewhat below the eutectic freezing point to a temperature below Ar1 and for a graphitic-carbon content from practically nothing to the original total carbon of the specimen (see Fig. 6). More especially we desired to locate the line in the stable diagram corresponding to the Acm line of the metastable system, which is designated by analogy, the Atm line (tm from temper carbon) ; also to determine the location of Aim with respect to Acm toward their lower extremities at Ar1 in order to determine whether or not graphitization is completed by the separation of an iron-carbon eutectoid analagous to pearlite in the iron-cementite system. This would involve further a comparison of the locations of the stable and metastable A1 points.

Jan 8, 1922

1 Healthy and active Local Section organizations are vital factors in promoting the vigor and growth .of the Institute 2 Activity on the part of Local Sections should be recognized and stimulated by appropriation of funds, from the Institute's treasury, and these appropriations should be as large as is consistent with the relative needs for other activities 3 As between different Sections, the amount of such appropriations should be based primarily on the extent of activities as reflected in the number and character of meetings held and the attendance of the members at such meetings 4 In making a request for funds for any year, the officers of a Local Section should submit a report on the printed form approved by the Directors at their meeting on November 19, 1937

Jan 1, 1952

1. Healthy and active Local Section organizations are vital factors in promoting the vigor and growth of the Institute. 2. Activity on the part of Local Sec¬tions should be recognized and stimu¬lated by appropriation of funds from the Institute's treasury;. and these appropriations should be as large as is consistent with the relative needs for other activities. 3. As between different Sections, the amount of such appropriations should be based primarily on the extent of activities as reflected in the number and character of meetings held and the attendance of the members at such meetings. 4. In making a request for funds for any year, the officers of a Local Section should submit a report on the printed form approved by the Directors at their meeting on November 19, 1937.

Jan 1, 1941

By Frederick Laist

This paper is a review of Montana reverberatory smelting practice covering a period of approximately fifty years, during which time the small furnaces that had been in use elsewhere for a century or more, without much change in size or method of operation, were revolutionized and were developed into the huge, continuously operating furnaces of today. A study of Montana practice is particularly instructive, since reverberatory furnace smelting for the production of copper matte received more attention there than in other smelting centers and many of the improvements that finally resulted in establishing the preeminence of this type of furnace over the blast furnace originated in Butte and Anaconda. The material in this paper was gathered from original sources, wherever possible, and all of the illustrations were made from original drawings, some of which have been simplified and worked over so as to be better adapted for reproduction. The aim has been to trace the modifications in design and operation which took place during the period in question—the reasons for the changes and the results achieved through them. For developments during the first twenty years, the technical literature of the period was freely drawn upon, but I am particularly indebted to W. M. Kelly, general foreman at the Anaconda Works, whose recollections and personal experience extend back to the early days. I wish to acknowledge the use made of publications of E. P. Mathewson, William Wraith and L. V. Bender, as well as information obtained here and there from friends and associates. The resume of Great Falls practice was compiled from correspondence, notes and drawings found in the files of the old Boston & Montana Co. and the tabulations showing the performance of furnaces at Butte and Anaconda are adapted from plant records and correspondence in the files of the Anaconda Copper Mining Company. The paper deals with some interesting comparisons that were made between furnaces operated under various conditions in connection with the Carson Case, and results obtained when using natural gas as fuel. This part of the paper may be considered original to the extent that these results have not previously been published.

Jan 1, 1934

By George K. Burgess, Robert A. Hadfield

1. Introduction.—The methods of production of sound steel ingots have been described in several papers read recently before this Institute. It was thought by Director Stratton, of the U. S. Bureau of Standards, and ourselves to be of sufficient interest and importance, as a further contribution to this subject, to compare the properties of rails rolled in one mill according to American practice, from several types of ingot of substantially the same chemical composition but cast by several processes; and to compare in considerable detail the properties of an ingot manufactured by the Hadfield special-feeding process and one of the usual type for rolling into rails. We are greatly indebted to F. W. Wood, President of the Maryland Steel CO., who made this investigation possible by kindly placing his rail mill at our disposal; and he and his associates at Sparrows Point did everything possible to make the experiment a success, including the execution of several of the tests and analyses. 2. Classification and Manufacture of Ingots.—Of the ingots used in this investigation, eight were made in Sheffield and furnished by Sir Robert Hadfield, and one was made and furnished by an American steel company,l as a comparison ingot, and was supposed to represent the usual type of ingot from which rails are made. The characteristics of the ingots are given in Table I. Ingots 1, 2, 3, and 4 were cast large end up and fed by the Hadfield method in the usual manner with charcoal and blast continued until the molten steel has set on the top of the head, say varying from 20 to 40 min. To ingots 1, 2, and 4 was added 0.1 per cent. aluminum, and to the nickel-chrome ingot, No. 3, 0.125 per cent. For sake of comparison, there were also included two ingots, Nos. 8 and 9, cast with the small end up and fed by

Jan 1, 1915

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.' Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz' to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""'"'"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15'F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By S. S. Marsden, S. A. Khan

Externally generated foam was injected continuously into short porous media. Both flow rate and pressure drop were measured. Liquid saturation was determined by electrical conductivity. Foam yuality I, expressed as the ratio of gas volume to total volume, was varied from 0.70 to 0.96. As measured with a modified fann VG Meter, apparent viscosity of this foam µa decreases with increasing shear rate but usually falls within the range of 50 to 500 cp. At a given shear rate, µa increases almost linearly with I-. When measured with a Bendix Ultraviscoson, kinematic pa is independent of V but absolute pa increases with T from about 3 to 8 cp. The effective permeability -apparent viscosity ratio ke/µa decreases almost linearly with V for porous media of high permeability, but the rate of decrease becomes less for tighter ones. The relative permeability-apparent viscosity ratio kr/µa us V data does not fall on a single line. The kr/µa ratio increases with liquid saturation in the porous medium and with surfactant concentration. Estimates of pa for foam in porous media vary from 30 to 100 cp. INTRODUCTION Although research on the development of a foam-drive, oil recovery process has been going on for almost a decade, most of the significant publications have appeared within the last several years. This illustrates well the rate at which interest in this process is accelerating. Bond and Holbrook 1 were the first to describe the use of foam to improve oil recovery in their patent of 1958. They proposed that an aqueous foaming agent slug be injected into the formation and that this be followed by gas to produce a foam in situ. Fried 2 studied the injection of foam into porous media which had already been subjected to conventional gas or water drives and found that gas could be used to drive a foam bank which would, in turn, displace additional oil in the form of an oil bank. He attributed the increased oil recovery to the high effective viscosity of foam flowing in porous media. His microscopic observations showed the importance of foam generation and regeneration within the porous medium. By injecting both air and aqueous surfactant solution, Bernard3 generated foams within the porous medium in which oil displacement was being studied. In a separate empirical test, he also measured the dynamic foaming characteristics of the same surfactants in water and/or oil. With some exceptions and for the seyen surfactants studied, there seems to be a qualitative relationship between the efficiency of liquid rlisplacrment and the dynamic foaming testtsed. This relationship was not consistent enough to eliminate the necessity of actual foam flood tests in porous media for surfactant selection. In a study basic to gas storage in aquifers, Bennett4 described the displacement of brine by foam in consolidated porous media. Among other things, he stated that the ability of a surfactant solution to foam is more important than the stability of its foam. The presence of a foam bank between the displacing air and the displaced brine improved both breakthrough and ultimate recovery. In a continuation of this work Kolb5 attributed the great reduction in surfactant solution production rate as displacement by air progressed to a decrease in relative permeability to gas. These several effects reported by both Bennett and Kolb can all be attributed to the high apparent viscosity of foam which was obviously flowing in the porous media. Bernard and Holm6 observed that gas permeability in the presence of foam was much less than in the absence of foam when both were measured at the same gas saturations. This reduction in permeability was proportionately greater for more permeable sands and sandstones than for the less permeable. Viscosities of the surfactant solution and air were used for their calculations rather than apparent foam viscosities. The foam stability increased with decreasing permeability, which was probably due to the natural regenerative properties of porous media, and the permeability reduction increased

Jan 1, 1967

By Frederic Laist

IN the spring of 1931 an experiment was made at Anaconda with a small reverberatory furnace, with which was combined a roasting shaft. The arrangement is shown in the accompanying drawing (Fig. 1) and requires but little explanation. The general idea was to roast .flotation concentrates, mixed with the proper fluxing materials, by dropping them down a heated shaft, from which the calcines would enter the smelting zone of the reverberatory furnace through an opening in the roof. The hearth of the reverberatory was 3 ft. wide by 21 ft. long. The roasting shaft was 3 ft. square inside and had an effective height of about 20 ft. . The reverberatory furnace was arranged so that it could be charged either directly through the roof with regular hot calcines, in the usual manner, or by means of the shaft, at the top of which were a feed-ing arrangement by which cold flotation concentrates, suitably fluxed, could be fed continuously and a pipe through which cold air was blown in. Means were provided for distributing the feed over the cross-section of the roasting shaft. At first a mechanical arrangement was used but later it was found that a simple cone served the purpose equally well and gave less operating trouble. On account of the small size of the equipment, it was realized that absolute capacity and fuel consumption figures would mean but little. It was not to be expected that ratios comparable to those obtained in large furnaces could be gotten, and the only way in which any idea could be obtained as to the possibilities of the combination furnace was to run it in parallel with the reverberatory furnace charged in the usual manner and operating without the shaft. The results of such parallel runs are given in Table 1. The amount of oil burned in the reverberatory was purposely maintained at substantially the same rate during both runs in order that the benefits resulting from the shaft might be gaged.

Jan 1, 1933

By W. C. Knoblaugh

Rotary kilns are adaptable to many fuels, but this paper deals principally with the use of powdered coal. The observations and conclusions presented are based on rotary kilns used in the manufacture of basic refractories for steel furnaces. Solid fuels are pulverized for two principal reasons: (I) ease of control, and (2) rapidity of combustion. By the use of pulverized coal, the operator can increase or decrease the fuel supply by small increments and with very little time lag between the change of control and the resultant change in the flame. This is extremely important in this type of furnace, as the temperature range for maturing the clinker is very narrow. By fine grinding, it is possible to increase the rate of burning of the coal, thereby liberating great quantities of heat within a small space in a short time. Under given conditions, temperature is a measure of the heat liberated per unit of time. To attain the temperatures of 2950° to 3150ºF., which are encountered in the manufacture of various steel-furnace refractories, it is estimated that it is necessary to liberate 125,000 to 175,000 B.t.u. per cubic foot of the burning zone per hour. The manufacture of dolomitic refractories is a ceramic process and, as is true in most such processes, the material must be subjected to a certain critical temperature for a certain length of time in order to complete the reaction. If the time of reaction is reduced, the temperature must be increased; in other words, if the rate at which the material flows through the hot zone of the kiln is increased, the temperature of the hot zone must be increased to compensate for this shorter exposure to the flame. Firing with Pulverized Coal Fig. I is a line drawing of a rotary kiln with the attendant equipment indicated in their relative positions. The kiln proper consists of a sloping, refractory-lined steel tube rotating slowly about its longitudinal axis (0.75 r.p.m.), and is countercurrent in operation in that the raw feed is introduced at the stack end and gradually approaches the zone of highest temperature at the lower end, where the fuel is introduced. Before 1930, the usual method of firing a rotary kiln was to store the coal in the pulverized form and then feed from this storage to the kiln as needed. This proved unsatisfactory and dangerous because of dust explosions and the inability to obtain an even feed to the kiln caused by arching of the coal in storage and flooding of the coal feeders. In later years the practice has been to store the raw coal and grind it as it is needed. Such a layout is indicated in Fig. I. The coal is stored in bins, charged from the top and drawn from the bottom into recording scales and then into some type of unit pulverizer. There are a number of good pulverizers .on the market, each incorporating features that the manufacturer considers outstanding.

Jan 1, 1948

By W. C. Knoblaugh

Rotary kilns are adaptable to many fuels, but this paper deals principally with the use of powdered coal. The observations and conclusions presented are based on rotary kilns used in the manufacture of basic refractories for steel furnaces. Solid fuels are pulverized for two principal reasons: (I) ease of control, and (2) rapidity of combustion. By the use of pulverized coal, the operator can increase or decrease the fuel supply by small increments and with very little time lag between the change of control and the resultant change in the flame. This is extremely important in this type of furnace, as the temperature range for maturing the clinker is very narrow. By fine grinding, it is possible to increase the rate of burning of the coal, thereby liberating great quantities of heat within a small space in a short time. Under given conditions, temperature is a measure of the heat liberated per unit of time. To attain the temperatures of 2950° to 3150ºF., which are encountered in the manufacture of various steel-furnace refractories, it is estimated that it is necessary to liberate 125,000 to 175,000 B.t.u. per cubic foot of the burning zone per hour. The manufacture of dolomitic refractories is a ceramic process and, as is true in most such processes, the material must be subjected to a certain critical temperature for a certain length of time in order to complete the reaction. If the time of reaction is reduced, the temperature must be increased; in other words, if the rate at which the material flows through the hot zone of the kiln is increased, the temperature of the hot zone must be increased to compensate for this shorter exposure to the flame. Firing with Pulverized Coal Fig. I is a line drawing of a rotary kiln with the attendant equipment indicated in their relative positions. The kiln proper consists of a sloping, refractory-lined steel tube rotating slowly about its longitudinal axis (0.75 r.p.m.), and is countercurrent in operation in that the raw feed is introduced at the stack end and gradually approaches the zone of highest temperature at the lower end, where the fuel is introduced. Before 1930, the usual method of firing a rotary kiln was to store the coal in the pulverized form and then feed from this storage to the kiln as needed. This proved unsatisfactory and dangerous because of dust explosions and the inability to obtain an even feed to the kiln caused by arching of the coal in storage and flooding of the coal feeders. In later years the practice has been to store the raw coal and grind it as it is needed. Such a layout is indicated in Fig. I. The coal is stored in bins, charged from the top and drawn from the bottom into recording scales and then into some type of unit pulverizer. There are a number of good pulverizers .on the market, each incorporating features that the manufacturer considers outstanding.

Jan 1, 1948