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By Richard Ageton

SALT bodies in the form of rolls, horses (sometimes called horsebacks), folds, wants and pinches1 have been encountered while driving entries and mining out rooms during the development of the potash mines in New Mexico. Superficially these sporadic salt occurrences appear to be much alike, but closer examination reveals individual characteristics, and after four years of observation it seems possible to divide them into three general groups that may tentatively be called "depositional," "erosional," and "structural." The data collected are not yet sufficient to permit forecasts of their probable location, so that the annoyance of having to mine salt instead of potash could be avoided or lessened. However, the information so far available appears to throw some light on the occurrence of the sylvinite2 bed now being mined, and it is as a progress report that the writer presents the results of his observations. The mines of the United States Potash Co. and the Potash Company of America are about 20 miles northeast of Carlsbad, in Eddy County, N. M. They are on the southwestern flank of the Permian salt basin, which underlies western Texas, Oklahoma and Kansas, south-central Nebraska, southeastern Colorado and eastern New Mexico. The cuttings from many oil wells and the cores from the potash tests drilled in this basin indicate that this salt series approached its greatest thick-ness (about 4000 ft.) in the southeastern part of New Mexico and the adjoining portions of Texas, and that the most advanced stages of

Jan 1, 1936

Olof Venstrom (communication to the Secretary*):—In order to do justice to a property, once the largest producer of copper in the world, which is now being reopened, with a fair promise of again becoming important, I beg to add a few words in connection with Mr. Souder's remarks on the El Cobre copper-mines. The El Cobre copper-mines were worked by the old English

Jan 1, 1905

By Richard V. Ageton

Salt bodies in the form of rolls, horses (sometimes called horsebacks), folds, wants and pinches1 have been encountered while driving entries and mining out rooms during the development of the potash mines in New Mexico. Superficially these sporadic salt occurrences appear to be much alike, but closer examination reveals individual characteristics, and after four years of observation it seems possible to divide them into three general groups that may tentatively be called "depositional," "erosional," and "structural." The data collected are not yet sufficient to permit forecasts of their probable location, so that the annoyance of having to mine salt instead of potash could be avoided or lessened. However, the information so far available appears to throw some light on the occurrence of the sylvite2 bed now being mined, and it is as a progress report that the writer presents the results of his observations. The mines of the United States Potash Co. and the Potash Company of America are about 20 miles northeast of Carlsbad, in Eddy County, N. M. They are on the southwestern flank of the Permian salt basin, which underlies western Texas, Oklahoma and Kansas, south-central Nebraska, southeastern Colorado and eastern New Mexico. The cuttings from many oil wells and the cores from the potash tests drilled in this basin indicate that this salt series approached its greatest thickness (about 4000 ft.) in the southeastern part of New Mexico and the adjoining portions of Texas, and that the most advanced stages of

Jan 1, 1938

By Richard V. Ageton

Salt bodies in the form of rolls, horses (sometimes called horsebacks), folds, wants and pinches1 have been encountered while driving entries and mining out rooms during the development of the potash mines in New Mexico. Superficially these sporadic salt occurrences appear to be much alike, but closer examination reveals individual characteristics, and after four years of observation it seems possible to divide them into three general groups that may tentatively be called "depositional," "erosional," and "structural." The data collected are not yet sufficient to permit forecasts of their probable location, so that the annoyance of having to mine salt instead of potash could be avoided or lessened. However, the information so far available appears to throw some light on the occurrence of the sylvite2 bed now being mined, and it is as a progress report that the writer presents the results of his observations. The mines of the United States Potash Co. and the Potash Company of America are about 20 miles northeast of Carlsbad, in Eddy County, N. M. They are on the southwestern flank of the Permian salt basin, which underlies western Texas, Oklahoma and Kansas, south-central Nebraska, southeastern Colorado and eastern New Mexico. The cuttings from many oil wells and the cores from the potash tests drilled in this basin indicate that this salt series approached its greatest thickness (about 4000 ft.) in the southeastern part of New Mexico and the adjoining portions of Texas, and that the most advanced stages of

Jan 1, 1938

By Friedrich Wellmer

INTRODUCTION The Ramsbeck Pb/Zn Mine is located in the northern Sauerland area of West Germany, 150 km N of Frankfurt and 120 km E of Cologne. This is a vein deposit which has been worked from the middle of the 19th century to 1974. About 15 million tons of ore were mined and milled. The ore district contains several vein deposits and is roughly 14 km in length and 4 to 5 km in width. The host rocks are strata of Lower Middle Devonian age. The strata strike 60° to 70° NE and where overturned have a dip steeper than the veins (Fig. 1). The galena-sphalerite mineralization is in quartz veins, which are mineralized where they cut the "Main Ramsbeck Quartzite" horizon, a very competent host rock. Vein structures strike at 65º to 75º, dip about 20° to 25º SE and cut the quartzite at approximately 60 m intervals. The main or "steep veins" within each vein structure dip at 10º to 80° SE with an average of 30° and are offset by thrust faults dipping 5º N to 40° S with an average of 5º S. "Flat veins" usually weakly mineralized occur in the thrust faults between the "steep veins", thus forming the overall step-like vein structure. The mineralization is very irregular and changes a- long strike and down dip. It consists of thin veins of pure sphalerite and galena with quartz and pyrite. The thicknesses of the pure sphalerite and galena veins

Jan 1, 1977

By W. F. Dietrich

Mineral fillers are relatively inert chemically under the conditions of use but have physical properties* that modify those of the materials • The properties. uses, and other data on 15 classes of important *The pro listed in the second edition of Industrial Minerals and Rocks.l A third edition of this reference is in preparation. in which they are incorporated. The mineral fillers considered in this article are asbestos, barite, clays, diatomite, crushed limestone, limestone whiting and lime, mica, silica, talc and soapstone, and pyrophyllite. Slate and stone, other than limestone and its derivatives, are excluded because, even though used in large quantities, they are exceptionally low-cost materials generally produced close to the area where they are used. Carbon black is excluded because it is manufactured from natural gas and more than 90 pct of the output is used in rubber; hence the factors for estimating requirements are easily evaluated. OVERALL GROWTH FACTORS Table I gives the population, retail sales, and value added by manufactures in the U. S. and in the eleven western states in 1954. These data are rough guides to the proportionate part of total U. S. markets for products containing mineral fillers that may be expected in a given area. For example, the population of the eight Mountain states in 1954 was 3.6 pct, and retail sales in these states were 3.8 pct of the U. S. total, but the value added by manufactures was only 1.3 pct of the U. S. total. On the other hand, the three Pacific Coast states, with 10.3 pct of the total population, had 12.0 pct of the retail sales and produced 9.6 pct of the value added by manufactures. On an industry-by-industry basis the correlation between the three guideposts will not be as close as shown in the 1954 data for the Pacific Coast states, but in the long-term view the continuing rapid population growth in the western states is certain to result in expanded industrial production at an even more accelerated pace, which will shorten the gap between local consumption and production in most major groups of manufactured consumer goods. Of course, there will always remain favorable areas for production of specific products. Such special situations must be individually analyzed. Fig. 1 compares the population trends in the U. S., the western states, and California with Real Gross National Product from 1910 to 1957, with forecasts to 1970. It is estimated' that the U. S. Real Gross National Product, as measured by the value of goods and

Jan 1, 1960

By Robert M. Jimeson

At the recent SME Fall Meeting in Salt Lake City, Robert M. Jimeson, Physical Science Administrator of the U.S. Bureau of Mines, cited the research programs underway in the Bureau's Division of Coal Research, and outlined their current status. These research programs have been selected by the Division because of their relative value and high probability of success in contributing to the conservation of the Nation's coal and to the expanded use of coal in current or new markets. Since about 50% of coal consumption in the United States is in the production of electric power, 20% in production of metallurgical coke, and over 20 % by industry in producing process steam and power, the Bureau has placed much emphasis on research that will maintain coal's leadership in these established areas. This emphasis is reflected in the projects discussed on these pages. Bear in mind that this survey is not all-inclusive. Other projects underway include studies on furnace performance factors, improved burner design, and other critical boiler work which can be used immediately by industry to improve efficiency of current practices in power generation; other investigations are aimed at reducing fireside deposits and corrosion of boiler and super- heater tubes, fly ash utilization, and control of SO, from flue gases (a major step in preventing air pollution). These plus many other projects during the past years have served to focus attention on the fact that the U. S. Bureau of Mines is presently making the largest single contribution to this Nation's coal research effort.

Jan 11, 1963

By Roshan Bhappu, Laszlo Dudas, Herman Maass

Introduction Chemical and mineralogical constitution play a very important role in the processing of ores because they dictate the method, either physical or chemical, for extracting the mineral or metal. Similarly, the mineralogical nature of the ore, especially the grain size of the valuable minerals, is very important in its processing. The fineness of the grain may be such that physical separation pro- cesses may be eliminated in preference to chemical techniques. In the past, very little attention has been devoted to the geo- logical and mineralogical occurrences which may be potential sources of ores by both the geologist and mineral processing engineer. On the one hand, geologists have devoted less attention to lower grade, complex mineral deposits, and, therefore, may have inadvertently curtailed an exploration 2rogra.m. On the other hand, the metal- lurgists have neglected to study in detail the geological environ- ments and mineralization of potential ores with the view of deter- mining the critical parameter that could assist in economically processing complex submarginal deposits. In the final analysis, a chemical processing technique converts the valuable metals to a mobile state under conditions similar to those which deposited originally in the host rock. The relationship between ore-genesis and chemical processing is close when the process of mineral or metal deposition in a particular ore deposit is understood--putting the metal in solution by reversing the process of deposition is re- latively easy. For this reason, some researchers and educators have been stressing the importance of ore-genesis, geochemistry, mineral equilibria, and ionic equilibria in studying and explaining the

Jan 1, 1974

SOUTHERN CALIFORNIA SECTION Executive Committee SEELEY W. MUDD, Chairman. C. COLCOCK JONES, Vice-Chairman. FREDERICK J. H. MERRILL, Secretary-Treasurer, 631 Higgins. Bldg., Los Angeles, Cal. RALPH ARNOLD A. B. CARPENTER A. B. W. HODGES WILLIAM F. STAUNTON The third meeting of this winter season tool: place in a private dining room of the Sierra Madre Club in Los Angeles on Feb. 1, 1916, at 6:30 p.m., 22 members and guests being present. In the absence of the Chairman, S. W. Mudd, the Vice-Chairman, C. Colcock Jones, presided. After an enjoyable dinner the meeting was called to order, and the first paper by Ralph Arnold on Conservation of Oil and Gas in the Americas was read by the Secretary. W. F. Staunton then read an important paper on The Influence of California Oil on the Mining Industry of the West. In this he touched upon the uses of oil as a fuel for generating power, especially in connection with the Diesel engine. This paper was discussed it some length by J. F. Mitchell-Roberts, R. B. Moran, F. H. Asbury and L. D. Godshall. The Chair then introduced Robert B. Moran of the California State Mining Bureau, Deputy Supervisor of Gas and Oil, for the' Los Angeles . District, who addressed the meeting on the work of his department. The meeting concluded with A. B. Carpenter's reading of a paper on The California Gasoline Industry by W. R.. Hamilton, Manager of the Ventura Refining Co. F. J. H. MERRILL, Secretary. ,

Jan 4, 1916

By Richard Ageton

SALT bodies in the form of rolls, horses (sometimes called horsebacks), folds, wants and pinches1 have been encountered while driving entries and mining out rooms during the development of the potash mines in New Mexico. Superficially these sporadic salt occurrences appear to be much alike, but closer examination reveals individual characteristics, and after four years of observation it seems possible to divide them into three general groups that may tentatively be called "depositional," "erosional," and "structural." The data collected are not yet sufficient to permit forecasts of their probable location, so that the annoyance of having to mine salt instead of potash could be avoided or lessened. However, the information so far available appears to throw some light on the occurrence of the sylvinite2 bed now being mined, and it is as a progress report that the writer presents the results of his observations. The mines of the United States Potash Co. and the Potash Company of America are about 20 miles northeast of Carlsbad, in Eddy County, N. M. They are on the southwestern flank of the Permian salt basin, which underlies western Texas, Oklahoma and Kansas, south-central Nebraska, southeastern Colorado and eastern New Mexico. The cuttings from many oil wells and the cores from the potash tests drilled in this basin indicate that this salt series approached its greatest thick-ness (about 4000 ft.) in the southeastern part of New Mexico and the adjoining portions of Texas, and that the most advanced stages of

Jan 1, 1936

By Charles H. Behre

This paper discusses education and training for economic geologists other than petroleum geologists. Candidates enter economic geology through liberal arts colleges, engineering schools and university graduate study. Whatever their backgrounds, rigorous courses are desirable-now conceded in theory, but not adequately recognized in practice. Besides basic sciences (each studied long enough to give a fair comprehension of its basic tenets), a functional command of English and two modern foreign languages is needed, as well as a broad understanding of mining, milling and metallurgy. A year of economics and finance is recommended. Surveying and drafting are essential skills. Yet geology should be represented in each term; otherwise the initial enthusiasm for the science, once contact is broken, may never be regained. A five-year curriculum is thus designed to take care of all major requirements and culminate in the M. S. degree. This curriculum reduces "cultural" courses below the average liberal arts requirements, but this is regarded as necessary. The pursuit of "culture" is assigned, as in most engineering and medical curricula, to extra college years or extracurricular time. To avoid the danger of over-crowding the schooling, the Doctorate in geology is preferred wherever possible. Its two added years should permit wider professional education; more browsing in "cultural" pastures; due attention to broader social implications; and some training in the research now increasingly required of the mineral industry. "In-course" training through cooperation between school and industry is especially advocated. The Institute should take the initiative in stimulating this practice.

Jan 1, 1947

By Raymond Mancha

The use of blower fans and tubina- for auxiliary face ventilation is a somewhat controversial subject. Most authorities agree upon the advantages of this system over the maintenance of line brattice for dead-end ventilation. They also recognize the system's disadvantages. However, there is considerable disagreement as to the proper relation of the advantages to the disadvantages. It is the purpose of this report to present the opinions of four authorities of diversified occupation and permit the reader to form his own opinions on the subject. ORsErvers Carel Robinson is a mining engineer consultant of wide repute, who has a background of operating experience. Thomas G. Fear is a mine operator whose present position is that of chief engineer for the Hanna Coal Co. at St. Clairsville, Ohio. E. H. Denny is chief of the Coal Mine Inspection Division of the U. S. Bureau of Mines, and is a very able engineer whose past experience well qualifies him to appraise this problem. Cloyd M. Smith, editor of the periodical Mechanization, is a ventilation consultant. For a number of years he was a member of the Mining Department of the University of Illinois and has studied mine ventilation for many years. It is Mr. Robinson,s opinion that closely spaced breakthroughs, although conducive to low gas accumulation past the last open crosscut during the driving of entries, are difficult to maintain and are constant Sources of fugitive air. Jute or canvas brattice is suitable for entry driving with

Jan 1, 1944

By Raymond Mancha

The use of blower fans and tubina- for auxiliary face ventilation is a somewhat controversial subject. Most authorities agree upon the advantages of this system over the maintenance of line brattice for dead-end ventilation. They also recognize the system's disadvantages. However, there is considerable disagreement as to the proper relation of the advantages to the disadvantages. It is the purpose of this report to present the opinions of four authorities of diversified occupation and permit the reader to form his own opinions on the subject. ORsErvers Carel Robinson is a mining engineer consultant of wide repute, who has a background of operating experience. Thomas G. Fear is a mine operator whose present position is that of chief engineer for the Hanna Coal Co. at St. Clairsville, Ohio. E. H. Denny is chief of the Coal Mine Inspection Division of the U. S. Bureau of Mines, and is a very able engineer whose past experience well qualifies him to appraise this problem. Cloyd M. Smith, editor of the periodical Mechanization, is a ventilation consultant. For a number of years he was a member of the Mining Department of the University of Illinois and has studied mine ventilation for many years. It is Mr. Robinson,s opinion that closely spaced breakthroughs, although conducive to low gas accumulation past the last open crosscut during the driving of entries, are difficult to maintain and are constant Sources of fugitive air. Jute or canvas brattice is suitable for entry driving with

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

TRE solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to 1300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. REVIEW OF PREVIOUS WORK The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available. According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar6 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwas3é reported large hydrogen solubility values for several compositions of copper- tin alloys, which appear to be in error.

Jan 1, 1944

By P. Bolsaitis, L. Skolnick

Vapor pressures of silver over ternary alloys of six different copper to gold ratios have been measured by means of the Knudsen effusion technique. The data obtained in the temperature range of 1330° to 1375° have been used to estimate the integral excess free energies of the ternary alloys and the activities of copper and gold. The results compare favorably to the predictions based on the electron cell model of alloys recently formulated by the authors. THE orifice effusion method for measuring vapor pressures of materials in condensed phases was first introduced by knudsen, and has since been used extensively for the determination of thermodynamic properties of condensed phases. The basis of the measurement is the effusion, through a small orifice, of vapor in equilibrium with a condensed phase. Assuming free molecular flow into high vacuum, the vapor pressure, P (in mm Hg), of the effusing species is calculated from the following equation:' where w (g) is the weight of effusing species lost during a run, t (sec) the time length of the run, A, (sq cm) the area of the effusion orifice, T ("K) the temperature at which the run is conducted, M the molecular weight of the effusing species, and k the Clausing factor, a constant that corrects for deviations from free molecular flow caused by the finite thickness of the orifice walls.17 The determination of partial and integral thermodynamic variables from vapor pressure data of ternary alloys is possible only if the vapor pressures of all but one component are negligible or can be esti-

Jan 1, 1969

By E. J. Efsic, C. M. Wayman

The fcc to bcc y to a transformation in an Fe-24.5 at. pct Pt alloy was studied and found to be martensitic. Large martensite plates are formed in this alloy which are ideal for crystallographic studies; the Ms temperature is about -5°C. Ordering of the parent phase prior to transformation to martensite causes a pronounced lowering of the Ms temperature. For the first time in the case of alloys of iron, measurements of the habit plune, orientation relationship, and magnitude and direction of the shape stvain have been obtained on preselected martensite plates. It is shown that by measuring the initial and displaced (as a result of the shape strain) positions of three or more non-parallel fiducial scratches on one reference surfice the maguitude and direction of the shape strain and the state of distovtion at the parent-mavtensite interface can be determined with a reasonable degree of accuvacy. The agreement between the phenomenolog-cal crystallographic theory of martensitic transformations and the experimental results habit plune, orientation relationship, and nlagnitude and direction of the shape strain) is essentially perfect, and is thought to be the best reported to date for iron alloys. THE comparatively few investigations on binary Fe-Pt alloys have been concerned with magnetic properties, ordered phases, and the equilibrium diagram itself. Various investigations have shown that the equilibrium diagram is of the open y field type; in addition there is a peritectic transformation, a minimum melting point, and three ordered phases: Fe3Pt, FePt, and FePt3. The results of a number of investigators1-6 have shown that the temperature dependence of the y to a (and reverse) transformation in iron-rich alloys is reasonably well-established. The Fe3Pt phase was first noted by Kussman and Rittberg,7 and its existence was later confirmed by Franklin et al,8 Steijn and Donahoe,9 and Berkowitz et al.10 The FePt phase was reported by Isaac and amman' and later confirmed by a host of others.3,6,7,12,13 Kussman and Rittberg7 noted the existence of the superlattice FePt3. Prior to 1956, the 1 to a transformation in iron-rich Fe-Pt alloys was termed "irreversible". In 1957 Klokholm and Donahoe" termed this transformation martensitic, presumably because of its occurrence at temperatures well below those where diffusion normally takes place. This observation served as a point of departure for the present investigation, and in the very early stages of the work to be discussed it was readily verified that the y to a transformation in iron-rich Fe-Pt alloys is indeed martensitic. Quite large martensite plates exhibiting the well-known surface tilt were observed. These plates are ideal in the sense that the boundaries between the parent and product phases were usually very straight. It thus appeared that Fe-Pt martensites would be ideal for crystallographic studies, and this was the purpose of the present investigation. Details of the crystallography of martensitic transformations (particularly for iron alloys) and the phe-nomenological crystallographic theories15-l7 have been discussed many times and thus will require very little elaboration here. The end result of these theories, given in matrix form, is

Jan 1, 1968

By A. J. Teplitz, R. J. Goodwin

A new type water shut-off for use in air drilling has been developed. The method has been 99 to 100 per rent effective in several different formations of inter-ranular-type porosity. Since costs for materials, time and equipment used are relatively small, the process should extend economies of air drilling to many new areas. The treatment involves a new technique for forming a water-inroluble precipitate within the pores of a rock. Advantage it taken of the difference in mobility of a liquid and a gas in porous media to achieve the greatest volume of precipitate in a given pore. Reactants selected for the laboratory (2nd field tests were aluminum sulfate solution and gaseous ammonia. This process has been tested in both intergranular and fractured-type porosities. It has consistently shut-of between 99 and 100 per cent of the water flowing from formations having intergranular-type porosity and perrlreuhilities ranging from a few millidarcise to over a darcy The treatment is not particularly suitable for shutting-off water from fractured formations although plugging of the order of 50 per cent or greater has been achieved in all such applications. Among advantages of the treatment are: (I) no reaction waiting rime after a relatively short placement time, (2) a low mate-rials cost of about $3/f1 of hole treated, (3) use of common service-type equipment for treatment, and (4) no unusual requirements for mixing and placement. INTRODUCTION In rotary drilling with air or gas it has been possible to increase bit life by tenfold and more than double rate of penetration over corresponding performance when drilling with mud. These factors have amounted to as much as 22 per cent savings on total cost of drilling a well. However, these advantages are rapidly lost when water is encountered in an air- or gas-drilled well because water interferes with the removal of cuttings from the hole and also gives rise to other difficulties. In attempting to combat water troubles, operators have commonly resorted to such measures as mist drilling, treatment with cement or chemicals, converting to conventional mud drilling, or setting casing. In many cases these measures have either been costly or ineffective. In an effort to overcome this problem, studies were undertaken to develop an effective and economical water shut-off technique for use in formations possessing inter-granular-type porosity. Extensive laboratory experimentation finally led to a unique method for producing a water-insoluble precipitate within the pores of a sandstone. The unique part of the treatment is use of a liquid and a gas to form the precipitate, and in this case the reactants used were aluminum sulfate solution and gaseous ammonia. The reaction between these two materials is shown in the following equation. Al2 (SO1)3 - 18 H20 6NH2? saturated Water- Solution Cat 2A1(OH)3 . n H20 3(NH4)2SO • n H20 Solid Solid That is, a solid precipitate consisting of aluminum hydroxide and ammonium sulfate is formed when ammonia reacts with aqueous aluminum sulfate. The aluminum hydroxide is insoluble in water and the ammonium sulfate, though soluble, can only be removed from the formation pores by diffusion—an extremely slow process. Although the precipitate formed by the reaction is not particularly firm, great strength is not needed for a precipitate to bridge and plug intergran-ular-type porosity. A flow path in such a system is extremely tortuous and involves a great variety of pore

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.' 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 Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By A. M. Gaudin, R. T. Hukki

PREVIOUS work on the principles of comminution has shown: (I) that the surface produced is proportional to work input (Rittinger law, 1a-3); (2) that there is regularity to the weight distribution of the fragments according to size.4-10 In this paper it is brought out that the surface on the fragments is distributed in definite and simple relation to size. The experimental work has involved: I. Construction of an apparatus capable of measuring the surface of mineral fragments independently of the chemical composition of the fragments and independently of the site of the surface; 2. Refining the methods available for measurement of particle size; 3. Designing and building a crusher capable of operating on very small quantities of mineral, if necessary on single crystals, and in such fashion as to minimize handling losses of material. Complete experiments have been carried out with massive quartz and individual quartz crystals. Partial experiments, lacking surface measurements, have been made with glass spheres, galena, sphalerite, fluorite, salt and coal.

Jan 1, 1944