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By John McGhee, Jack Newcombe, M. J. Rzasa

A series of water floods was made on laboratory prepared unconsoli-dated sand columns to study the effects on oil recovery of the solid-water-oil contact angle, the oil-water interfacial tension, flood rate, and oil viscosity. A procedure was developed for treating silica sand with silicone polymer to produce surfaces of varying degrees of wettability as evaluated by measuring the contact angle on a flat silica plate that had been simultaneously treated with the sand. Fluid interfacial tensions were changed by the use of surface active agents in the flood water. Water-wet, oil-wet, and intermediate wettability systems were studied at high and at low values of interfacial tension, at several flood rates, and with oils of different viscosities. For both oil-wet and water-wet systems and a low viscosity oil, recoveries were functions of the oil-water interfacial tension; also, increase in flood rate resulted in increased oil recoveries. High interfacial tension floods were more efi- cient than low interfacial tension floods on water-wet systems, while low interfacial tension floods were more eficient on oil-wet systems. Intermediate or neutral wettability systems were less sensitive to rate of flood advance and interfacial tension than either oil-wet or water-wet systems. The eflects of surface forces on oil recovery for high viscosity oils were not so well defined as for low viscosity oils. INTRODUCTION Reservoir rock surfaces vary in their wettability1, some being water-wet while others are apparently oil-wet. The factor of wettability enters into reservoir performance in both primary and secondary recovery, and into laboratory measurements of capillary pressure, connate water saturation, and relative permeabilities.' In theory, the degree of wettability is measured by the contact angle for the system solid-water-oil. A water-wet system is defined as one in which the advancing water contact angle is less than 90". An oil-wet system is one in which the advancing water contact angle is greater than 90°.3 The surface forces in a solid-water-oil system are related by the Young-Dupree equation as follows4: These surface forces are commonly expressed as the difference in adhesion tension, or the product of the water-oil interfacial tension and the contact angle. If the contact angle is less than 90°, the adhesion tension difference is positive and oil displacement by water from a solid surface will be spontaneous and favored by a high oil-water interfacial tension. If the angle is greater than 90" the displacement will not be spontaneous but will require less energy the lower the oil-water interfacial tension. The contact angle and interfacial tension also appear in the capillary pressure equation5: PC = 2ocosejr .... (2) The quantity cos was used by Rapoport and Leas6 s a factor in the generalized form of their "sealing coefficient." Warren and Cal-houn' presented the results of cos on oil recovery in oil-wet systems and correlated their data using a "scaling coefficient" suggested by Jones-Parra and Calhoun.8 The "sealing coefficients" were advanced to help correlate the effects of the variables influencing oil recovery by

Jan 1, 1956

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By D. E. Furman

The thermal coefficients of linear expansion for several stainless steels have been determined over the temperature range from —300° to 1000°F. The steels studied include types 301, 304, 316, 347, 310 and 330. This wide selection of compositions allows an insight into the effects of austenite stability and alloy content on the expansion characteristics. THE recent increased use of materials in low temperature applications has created a field for which the properties of austenitic iron, chromium, nickel alloys are particularly suited. Tensile and impact values of stainless steels at subzero temperatures have been made available in the technical literature but, as yet, little information has been published with respect to expansion characteristics. In order to supply this need, a study was made of several of the more common compositions. Those selected were types 301, 304, 316, 347, 310 and 330 stainless steel. Both the mean and instantaneous coefficients of linear expansion were determined over the temperature range from —300°F to 1000°F. Procedure The materials used were commercial grades with the exception of type 301 which was made in a 10# high frequency furnace. The compositions are listed in table I. All steels were given an anneal at 1950°F for 30 min and water quenched prior to machining the expansion specimens. Expansion readings were taken on specimens 0.250 in. in diam by 4.000 in. long with a fused quartz tube expansion apparatus similar to that described by Hidnert and Souder.1 Temperature measurements were made with a chromel-alurnel thermocouple calibrated for use at subzero temperatures. A bath of propane was used for temperatures from —300° to —100°F and one of alcohol from —100°F to room temperature. These baths were contained in large mouthed Dewar flasks and cooled to the desired temperature levels by passing liquid nitrogen through glass cooling coils placed in the flasks. The baths were stirred constantly for temperature equalization and were heated by immersing metal rods which were replaced frequently enough to give a heating rate of approximately 150°F per hr. A resistance wound furnace was used for heating from room temperature to 1000°F and throughout this range rates of about 450°F per hr were maintained. The furnace was designed so that the temperature gradient over the specimen was within 5°F. In most instances, the expansion readings were taken during heating from —300° to +300°F at

Jan 1, 1951

By J. F. Wolff

EXPLORATION of Lake Superior iron ores is done principally by drilling. The soft iron ores are churn drilled and the harder ores are diamond drilled. In exploratory work in the harder formations, where the diamond drill is used, the sample comprises both core and cuttings. The care given in handling and preserving the core depends on the im-portance that may be attached to certain characteris-tic strata in different formations. The following instructions for the care of core samples are issued by the Oglebay Norton Co. for diamond drill work done for them on the Gogebic Range of Michigan: The driller shall be careful upon removing the core from the core-barrel to keep the core in exact order. Not only should the pieces of core be kept in exact relation to each other, but care should be used not to turn them end for end. Core should be placed in the core-box from left to right in each row. Each drill should be furnished with small, hinged cover core-boxes, and each drill should be well supplied with empty boxes. Core remaining at the drill when the drillers are not working should be locked up. The practice of picking sample pieces of core and carrying them away from the drill to be examined in better light, or shown to someone else, is unnecessary and prohibited. The reason for this is that these pieces are seldom returned to the core-boxes and valuable information or "markers" may be lost. If the inspector suspects that a critical point is reached in the drilling and he cannot determine at the drill, he should remove the entire core-box and see that the drill is immediately furnished with an empty core-box. It is customary to split the core longitudinally so that one-half may be ground to a pulp for analysis and the other half may be kept for future inspection. The core should be filed in permanent core-boxes, properly labelled, if the core is to be kept in exact order as taken from the core-barrel. Otherwise, it is often filed in tin boxes inn the way that sludge samples are filed. To obtain the average analysis, the core and cutting samples obtained in the same run are analyzed separately and the analyses are combined in the proper ratio.

Jan 9, 1922

By L. J. Buteau, R. E. Reed-Hill, W. A. Slippy

In a zirconium {1121} twins tend to have coherelzt boundaries and thus do not usually taper to a point when they intersect a grain boundary. Under the proper conditions, a (1121) twin may deform a boundary in such a manner as to clearly rcveal the twinning shear. Measurements of these grain-bounrlary rotatzons yield a value of 0.63 for the (1151) twinning shear. The magnitude of the observed shear and its shear sense are in excellent agreement with the assumption that the second undis-torted plme (K2) for this form of twinning is the basal plane (0002). The present value of the tzvinninz shear, which is approximately three limes larger than Rapperport&apos;s value? is in excellent agreement with reported results of Sokuskii and Prolsenko.5 RECENTLY westlake&apos; reported a study of the twinning modes of zirconium based on ~ap~er~ort&apos;s2 values for the twinning elements. He observed that two of the modes, (1012) and {1122), can be explained by relatively simple dislocation models. A workable model for (1121) twinning, however, proved to be very complex and questionable. Because Rapperport&apos;s second undistorted plane, (K2), for (1121) twinning has large indices, {ll2l6), it is possible that the difficulty in defining a model for (1121) twinning lies in an incorrect value for K2. A measurement of this twinning element has therefore been made, using a method based on observations of the shear displacement of grain boundaries at positions where they are intersected by (1121) twins. EXPERIMENTAL PROCEDURES The zirconium specimens were deformed in tension on an Instron machine either at the temperature of liquid nitrogen (77ºK), or prestrained at liquid nitrogen temperature and then further deformed at room temperature. Straining at 77°K was employed in order to nucleate (1 121) twins in large numbers, since simple ropm-temperature tensile deformation favors (1012) twinning. Specimens were machined from 1/2-in.-thick plate. The material was arc-melted sponge zirconium annealed to an ASTM grain size 4 and containing, in parts per million, 380 Fe, 880 0, <40 Hf, 32 N, and < 5 H. The specimen gage length and diameter were 1.25 and 0.130 in., respectively. To insure a gage section initially free of twins, the last 60 thousandths of the specimen diameter was removed by acid machining.

Jan 1, 1963

By W. M. Corse

I bring this investigation to your attention to emphasize the needless waste attendent upon the use of tin plate with an unnecessarily heavy tin coating. With our present knowledge, we are unable commercially to produce coatings as light as the lower weights used in this test. If, however, future research should develop means to this end, the resultant product would meet all practical requirements, and a very considerable saving in pig tin would result. DISCUSSION G. H. Clamer.-—The National Canners&apos; Association is studying the action of fruit juices, etc., on solders. Of course these tests will take quite a long time, and we hope by that time the war will be over and there will be no need for conserving tin for war purposes. Germany for a great many years has prohibited the use of more than 37 per cent. of lead in alloys used in contact with food products. The eutectic composition is 37 per cent. of lead and 63 per cent. of tin; alloys containing more than that percentage of lead have some free lead. J. W. Richards,&apos; South Bethlehem, Pa.—A great deal of conservation can result from the packing of dry foods in cartons and in fiber packages instead of using sheet tin. Many of the boxes used for packing things other than food are frequently made of sheet tin because it prints and lithographs well; these could be made of sheet iron coated with copper or some other substitute metal which prints equally well. The Aluminum Bronze Industry W. M. CORSE,† Mansfield, Ohio.—The conservation of tin, in view of the shipping situation, is one of great importance. Several methods of conservation can be employed: 1. Reduction of the amount of tin in an alloy or compound. 2. Substitution of an entirely different metal or compound for tin. 3. A combination of the first and second methods. The second method is the one that I wish to discuss. Metallic aluminum, has been known for a long time, and its use in copper alloys was discovered about 1855 by Lord Percy. The high cost of production of metallic aluminum retarded its commercial development, and it was not until the discovery of the electrochemical processes for its production that it came to be known as a common metal. I have been particularly interested, for the past few years, in working with the alloy known as aluminum bronze, which is usually composed of approximately 90 parts of copper and 10 parts of aluminum, by weight.

Jan 1, 1919

By Harry H. Power

WHILE the attention of all engineering branches is focused today on changes and improvements in the several curricula, we are concerned here with the many questions arising in industry and college concerning the preparation for the petroleum engineering profession. The succession of problems confronting the petroleum engineer demands a degree of versatility not ordinarily encountered in other professions. As a consequence, the student cannot acquire mastery of all the several engineering branches represented in field practice, and as an alternative, he has learned to appreciate the value of thorough training in the basic or fundamental sciences as a preliminary foundation for professional work. While our attention is directed primarily to the training of engineers in educational institutions, it is necessary that the ultimate education of the professional engineer be kept in mind. It is apparent that his success as an engineer is limited not only by his educational and job experience, but by his native endowments: mentality, personality and health. The engineer&apos;s lack of job experiences often proves as much a handicap as the lack of adequate college training. If the final product proves to be satisfactory, both industry and technical institutions are to be congratulated. However, if the product is found wanting, the one most responsible should be apprehended. FITNESS FOR PROFESSION For the most part, students of engineering colleges have had their interests in applied science awakened at a relatively early age. Many of them entered college as a convenient means of acquiring a technical education, but undoubtedly would have had better prospects in a shorter program offered by institutions of noncollege grade. The activating motive of practical interest is also strong in students suitable for college training, but in many cases an intellectual interest must be awakened in order that it may survive graduation. Numerous engineers believe that this progressive process of selection and determination of career aims is one of the essential services rendered by the engineering colleges. Industrialists, who are more interested in quality than quantity of petroleum engineering graduates, have pointed out the good that should result if more emphasis were given to the work of eliminating the misfits. They also point out the protective measures that have been taken by other professions for the betterment of professional standards. Mention has been made of the beneficial results to be obtained by collective determination of the market for the products of engineering schools, particularly in that the students unsuited to the profession would have an opportunity to prepare themselves for employment more suited to their personalities and other qualifications. In the event that such a system of coordinated personnel direction is developed by the

Jan 1, 1941

By Jasper L. Stuckey

HISTORY IT is not known when kaolin mining was first begun in North Carolina. Evidence, in the form of excavations and primitive tools, indicates that some of the deposits were worked in prehistoric times. It has been suggested that the prehistoric mining was for mica, but the workings were all in altered or partly altered pegmatite material and the dumps do not represent the amount of material removed. Some of the early openings may have been made in search of kaolin or semi-kaolinized feldspar which was sold to English1 traders along the coast and used in some of the early English porcelains. In 1944,2 an application was made for an English patent to produce porcelain from an earthy mixture obtained from the Cherokee Nation in North America. It is well established, however, that the occurrence of kaolin in western North Carolina was known in England by 1767. In that year, Josiah Wedgewood sent T. Griffiths3,4 to what is now Macon County, North Carolina, to secure a supply of kaolin for use in England. Griffiths diary, now in Etruria Museum, Stokes-on-Trent, contains a most interesting account of his experience. Kaolin was discovered at St. Austell, England, shortly after the voyage of Griffiths, which probably accounts for the lack of further interest in American kaolin. Between 1767 and 1888, there are no records of kaolin mining in North Carolina. In the latter year, however, mining was begun near Webster, Jackson County, and, in the intervening period, has become an important industry. For some 20 years, kaolin mining was carried on chiefly in Jackson, Macon, and Swain Counties. About 1904, it was begun in the Spruce Pine district and for the past 20 years most of the kaolin mined in the State has come from Avery, Mitchell, and Yancey Counties. DISTRIBUTION The kaolins of North Carolina are limited in occurrence to the Piedmont Plateau and Appalachian Mountain area of the State. While kaolins are widespread in the Piedmont Plateau, having been prospected for in Rutherford, Cleveland, Gaston, Granville, Lincoln, Catawba, Iredell, Richmond, Moore, Randolph, and Montgomery Counties, the production from that area has never been important. The known deposits of commercial importance are limited entirely to the mountain area of the State. While kaolins occur widely distributed throughout the mountain area and have been prospected for in many counties of that area, commercial production has come chiefly from two districts. One of these includes Jackson, Macon, Swain, and Haywood Counties. The other includes Avery, Mitchell, and Yancey Counties. GEOLOGY With few exceptions, all the known kaolin deposits in North Carolina contain

Jan 1, 1947

By H. B. Pulsifer

One of the most common basic open-hearth furnace products is a simple carbon steel with a carbon range from 0.05 to 0.15 per cent. The material is widely used for sheets, tubes, bars, wire and the innumerable special objects of secondary fabrication. The properties of the material vary over wide ranges, depending on the more exact composition and details of manufacture or treatment that affect its structure. The present paper is a review of those properties and structures that have been found by studying this steel as used in the cap screw industry. At first glance this might be thought a narrow application of the steel, but, since the industry uses the material in the cold-worked, annealed and heat-treated conditions, the title of the paper may be excused for its comprehensiveness. Yet, in studying the wide ranges of properties and structures that preclude a more specific title, there can be no suggestion of completeness or finality. Even a summary of a few years&apos; work is no more than a preliminary survey of a field that will be fertile in scientific data and industrial products for many years to come. An outline of the structures will be given first, then a list of the previous contributions that are at hand and finally some details of the work and related problems, especially concerning this low-carbon steel in the surface-hardened condition. Wire Used in Manufacture of Cap Screws The wire that is used for making cold-upset and roll-threaded cap screws has been cold-drawn from hot-rolled rods that were pickled and limed. The common sizes used in the industry range from 0.185 to 0.750 in. dia., the exact diameters depending on the plant practice and having the usual tolerances of 0.002 in. for the smaller sizes and 0.003 in. for the larger sizes. The carbon range, by pit analysis, is usually between 0.07 and 0.12 per cent. Manganese should be within the usual 0.30 to 0.50 per cent. range. Sulfur rarely exceeds 0.045 per cent. and phosphorus seldom exceeds 0.030 per cent. Silicon is usually below 0.03 per cent. but in the silicon-killed steels may be in the customary 0.10 to 0.25 per cent. range. Rimmed steel is not considered most suitable for cap screws that are cold-headed or for parts that are to be surface-hardened.

Jan 1, 1931

By Raymond B. Ladoo

ABRASIVES include the substances, natural or artificial, that are used to grind, polish, abrade, scour, clean or otherwise remove solid material, usually by rubbing action but also by impact (sandblasting, for example). They do not include abrasive tools-for instance, lathe tools and files-or polishing agents such as waxes, which act by filling pores. Detergents and cleaners whose action is chemical rather than physical are omitted although some chemical action polishes and cleaners may also contain solid abrasives; for example, many metal polishes. GENERAL CONSIDERATIONS The most important physical properties of materials that qualify them for use as abrasives are hardness, toughness (or brittleness), grain shape and size, character of fracture or cleavage, purity or uniformity. For making bonded grain abrasives such as grinding wheels, additional important factors are stability under high heat and bonding characteristics of grain surfaces. The economic factors of cost and availability are always important. No one single property is paramount for any use. For some uses extreme hardness and toughness are needed, as in diamonds for drill bits; for others, the factors of greatest importance are hardness and ability to break down slowly under use, to develop fresh cutting edges when grains become worn-for example, in garnet for sandpaper, neither highly cleavable or friable grains nor extremely tough grains

Jan 1, 1949

A Little Book on the Assaying of Gold, Silver, Copper, and Lead. Also on How to Assay and Work profitably All Minds of Metal. Complied with great care for the benefit of all mintmasters, assay masters, gold= smiths, miners, and dealers in metals.

Jan 1, 1949

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe&apos;s formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade&apos;s exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.&apos; The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf&apos;s CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

AVING started to tell you of working potter&apos;s clay for making crucibles and shells, the wish came to me to tell you of the practice of this art also. Although it may seem at first glance to be outside the order and purpose of my writing, he who considers well will see that it is not unrelated to it but proper, since it is wholly dependent on the agency and power of fire if it is to be brought to its perfection. Moreover, the potter&apos;s glazes and colors are all substances of various metals or impure minerals and therefore belong to fire. Since it is my intention to treat of fire, minerals, and metals for you, I surely should not have omitted this, particularly because it is a necessary art which enriches and is greatly praised both for its ingenuity and its beauty. The art of the potter has two sources as its principal basis. One comes from the art of design, the other from various alchemical secrets and elemental mixtures. In regard to these, I find that, in my opinion, all this art depends in the last analysis on four things: on good judgment in general, and on the art of design so as to be able to make the vessels beautiful and of good shape, as well as to ornament them with painting; after baking them well the first and second times, the next thing is to know how to make and apply the glaze well and to paint them with varied and appropriate colors. The fourth is to see that you have good, fine clay without small stones or lumps-indeed this is to be considered as the first thing. Now this that I have called clay is what many call cretaceous earth and some call argil. It is found and dug up when the masters wish to make use of it and is put in a container to be moistened. When it is moistened, it is beaten on a bench with an iron rod and very well prepared. Mixing it carefully, every small stone, lump, or other hardness that it contains is removed and cleaned away. Then a shaft [145V] of iron is fitted as the journal in a large wheel. On the other end of the journal a small wheel is made which forms an instrument for working that is called a lathe. Having put some clay on this, it is made to rotate by pushing with one foot, and, by rotating it, vessels are worked into a pleasing shape and size. Then they are taken off and put on a board to dry. After drying artificially or naturally they are painted red,

Jan 1, 1942

At a time when Congressional stiffening of health and safety regulations in the nation&apos;s coal mines seems all but an afterthought, when the problems confronting both mine operator and worker are being tossed about like a pigskin in an Australian- rules football match, what could be more appropriate to the times than to incorporate a discussion on these matters into the proceedings of an annual coal meeting. Integration of both technical and topical discussion provided the strength for this 28th Annual Meeting of the Central Appalachian Section of the AIME, convened at the The Greenbrier, White. Sulphur Springs. W. Va., Oct. 31-Nov. 1. Three technical sessions prepared for the occasion were served to those in attendance. First of these was held on Friday morning. Rendered excellent coverage, topics included Roof Structure Analysis at Blacksville No. I, presented by David Eyer, Christopher Coal Co.; Methane Monitors (evolution and evaluation of present day detection equipment); and Instantaneous Control Reaction to Mine Fires and Explosions, in which Elmer A. Fike illustrated the point quite vividly by showing a film on the potential of such control equipment. Indeed, the ability to snuff out a mine fire before it is allowed to spread even beyond its own igniting sparks speaks very well for itself. However, Fike hastened to point out that certain difficulties had to be overcome before these "fire watchers" could be implemented successfully in mines. These "bugs," inherent in virtually all coal mining environments, include ignition of sulfur pockets on mine facings and delivery of sparks on trolley rails, both of which may impede the accuracy of such control monitors.

Jan 12, 1969

By Sylvain J. Pirson

The question of the interpretation of apparent resistivity curves is still a much disputed subject although the discussion has been going on for several years, mainly since Gish and Rooneyl made their first measurements on the Tidal Basin at Washington, D. C. As a first approximation, they interpreted the depth to a horizontal discontinuity in terms of the electrode spacing at which a maximum or a minimum occurs in the resistivity curve. Later on, Lancaster-Jones2 proposed a closer approximation of depth determination by evaluating the depth to a horizontal discontinuity as the two-thirds of the electrode spacing at which a point of inflection occurs in the resistivity curve. An accurate determination of the depth was recently proposed by Tagg3 for a two-layer problem. It is a graphic solution of the problem by means of charts calculated from the formula of the apparent resistivity based on the theory of electrical images. Tagg&apos;s method is theoretically sound but the fact that the layers have been assumed to be homogeneous and isotropic must not be overlooked. Abusive use of the method has been made by geologists who have failed to recognize the fact that nature offers only few cases where the conductivity of the rocks may be assumed to be the same parallel and perpendicular to the bedding plane. Actually the ratio of the two resistivities in those directions may take values ranging from one (isotropic medium) to three for shales. In such conditions Tagg&apos;s method leads to disappointments. A method recently advocated by Manhart4 and Tattam6 forces Tagg&apos;s method to give a solution where manifestly the case under

Jan 1, 1934

By Frederick Rhines

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick&apos;s law (equation 1 below), ? in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick&apos;s law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activa-tion heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. Much of the argument concerning the properties of metals that deter-mine D and Q has been drawn from data in which variations of the quan-tities with concentration are unknown, for these data- have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concen-trations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick&apos;s law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick&apos;s law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938