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By F. W. Davis

SOME idea may be gained of the tremendous consumption of refractories by the open-hearth steel manufacturers from a statement made by A. T. Green at a meeting reported by T11.e Industrial Chemist of London, as follows: "At a very progressive steel plant in the Midlands, with a battery of five open-hearth furnaces working. twelve months and making 3000 tons of steel per week, the cost of refractories per ton of steel produced averages about $0.50 for the actual open- hearth casting and $0.12 for those operations incidental to the rolling of the metal." .These figures, when translated into the annual tonnage of steel, represent a very considerable expenditure.

Jan 1, 1930

By T. M. Girdler

INDUSTRIAL progress and development in this country from the earliest daps to the present has proceeded at an ever-quickening pace. Yet during recent decades the nature of our industrial progress and development has undergone a change of great significance. The earlier days were a period of tremendous expansion. Population was increasing by leaps and bounds. Vast areas of new land were being .2 opened to settlement. And almost boundless new sources of timber, coal, oil, ores, and power were being opened to ever-expanding markets. Today, however, that picture has al- most completely changed. Today, with population increase tapered way off and the opportunity for free expansion into western frontiers gone, the great industrial development of our country continues on a vastly different front. Industrial progress and development today rest on a foundation of technology. The key- stone is research. Our frontiers to- day are frontiers of sciencec

Jan 1, 1939

By J. R. Dunn

Planning quarry operations and control of the quality of rock materials at Hudson Cement Co. at East Kingston, N. Y., are special problems because of multiple uses for the stone and the great structural complexity of the rocks. Problems have been largely solved by detailed geologic work. These geologic studies have paid dividends in long and short range planning, in assessment of reserves, in vastly reduced cost of chemical analyses, and in reduced drilling costs. Limestones of the Hudson Valley outcrop along the Hudson River from Albany to Kingston. Old established cement companies are located just south of Catskill and just east and southeast of Hudson, N. Y. The new Atlantic Cement plant is being constructed at Ravena. Hudson Cement located at East Kingston, is a newcomer and is closest to the New York metropolitan area (Plate I).

Jan 11, 1961

PUBLIC hearings began before the Committee for Reciprocity Information on May 24, 1950, for the purpose of unearthing data and opinion that will be helpful in the forthcoming reciprocal tariff and other trade-barrier negotiations at Torquay, England, on September 28th of this year. The conference this fall will constitute the "third round" of tariff negotiations under the General Agreement on Tariffs and Trade concluded at Geneva in 1947. The United States plans to negotiate with 17 other countries on possible tariff modifications on various articles all the way from baby carriages and bottle caps to lead and zinc-bearing ores. On May 31, June 1 and June 2, spokesmen appeared before the Committee for Reciprocity Information on behalf of the domestic lead and zinc mining industries. Producers of these metals protested the inclusion of paragraphs 391 (lead-bearing ores, dust and mattes), 392 (lead bullion, lead in pigs and bars, and scrap lead), 393 (zinc-bearing ores of all kinds), and 394 (zinc in blocks, pigs or slabs, and zinc dust) of the Tariff Act of 1930, as amended in the list of articles to be considered for possible tariff concessions at Torquay. It was pointed out that although operating costs have more than doubled since 1939 tariffs on these metals were actually higher in that year than at present. This, coupled with the detrimental effects of the recent series of devaluations, has sounded the death knell for a substantial number of domestic lead and zinc mines-a most undesirable development in the face of the ominous international situation, according to these spokesmen. It was urged that higher rather than lower tariff rates are needed on these metals. The opinion was expressed that it was inconsistent to foster a high living standard in our western areas and then, once it is attained, to undermine that condition by minimizing the protection that was partly responsible for it. The main theme of some arguments implied that although every effort should be made to close the "dollar gap" abroad, serious consideration must be given the methods employed lest our national security position be jeopardized in the process. The House Committee on Foreign Affairs completed hearings on H. J. Res. 236, to provide for United States membership and participation in the International Trade Organization. Hearings began on April 19th and ran for over five weeks. Many witnesses from industry and government presented voluminous testimony, which will not be available for public distribution for several weeks. However, it is no secret that the most controversial provisions of the Draft Charter of the ITO are: (1) Article 17 (Chapter IV on Commercial Policy) which would obligate members to negotiate for the reduction of tariffs and the elimination of trade preferences; (2) Article 20 which would prohibit the use of quantitative restrictions for protective purposes; (3) Article 16 which promulgates rules to implement the principle of non-discrimination in international trade; and (4) provisions permitting the use of protective measures for promoting economic development, particularly in backward areas, even though such provisions are inconsistent with those of the three articles cited above. United States membership in the International Trade Organization is essential to the successful operation of that body in view of this country's position as the economic giant in the present international trade pattern. Many countries are reluctant to take any action toward the ratification of the charter until it is known what course America will pursue. However desirable or undesirable the ideal of free multilateral trade may be it is unlikely that this Government's participation in the ITO will materialize soon. Advices in Washington indicate that H. J. Res. 236 will not be enacted during the present session of Congress. The legislative pattern designed to secure Congressional approval of the ITO is similar to that of the St. Lawrence Seaway project. The Seaway project was pending in treaty form for several years before the Foreign Relations Committee of the Senate and when the Administration decided to incorporate this project into bill form it was found that, while it passed the House promptly, the Senate decided to pigeonhole it because of the obvious intent to circumvent the constitutional prerogative of the Senate to advise and consent to the ratification of treaties. The ITO bill may be slated for a similar fate. It is deemed essential by western Senators and Congressmen that the present session of Congress enact some form of mining legislation before its adjournment, now set for July 31st. These legislators from prominent ore-producing states do not desire to return to their home areas in the fall emptyhanded. Aside from that, it is entirely superfluous to reiterate the necessity for maintaining a healthy domestic mining industry as a bulwark against a sharp rise in the temperature of the "cold war". Now that S. 2105 has failed a new bill is taking shape in the Senate Interior and Insular Affairs Committee. It is similar in language to H. R. 8221 (to encourage the conservation and development of the mineral resources of the United States) reported by the House Public Lands Committee on May 3, 1950, but so far has failed to receive approval of the House Committee on Rules. There are some qualified observers in high circles in Washington as well as in the mining industry who favor a tax incentive program to stimulate investment in mining enterprises, as opposed to a conservation and exploration program. The Bureau of Mines and the Treasury Department have undertaken a joint study to determine the need for modification of the tax laws as they apply to mining. The study is scheduled for completion before the end of the year, and appears to be supplementary to the investigation initiated by the National Minerals Advisory Council which culminated in the submittal of recommendations to the Secretary of the Interior in December 1949. The "cold war" is largely responsible for the increased demand for metals. Stock-pile purchases and heavy industrial demand due to military needs distort markets and disrupt normal price trends. Such activity has an unhealthy influence on metal production, luring some producers into a state of dependency on the continuation of this condition. When stock-pile objectives are met sometime in the future purchases must then come to a halt unless international "fireworks" are touched off. It can only be hoped that technological improvements and further mechanization of mines coupled with the stimulus of a rising population will offset the anticipated drop in industrial demand and cessation of stockpile purchases when the international crisis abates.

Jan 7, 1950

By R. W. Vander Laan

Conneaut has a long and illustrious history as a major Great Lakes port for coal and iron ore. The first dock was built in 1892 for unloading iron ore from the Mesabi Range for shipment to the Pittsburgh steel mills via the Shenango & Lake Erie Railroad, later to become the Bessemer & Lake Erie Railroad. The Pittsburgh & Conneaut Dock Company was incorporated in 1893. The world's first Hulett automatic ore unloader was constructed at Conneaut in 1899. Steam operated, it was the model for the giant electric Huletts used today, named after its inventor, George Hulett, who was a Conneaut resident.

Jan 3, 1974

By Carl Altstetter, Emmanuel deLamotte

The influence of an external stress and plastic deformation on the allotropic transformation of single crystals of a Co-30.5 pct Ni alloy was investigated. Experimental results were obtained from dilatometry, X-ray diffraction, and optical and electron microscopy. The effects of stresses could be conveniently divided into three stress ranges. In range I, from 0 to about 400 g per sq mm, the specimens exhibited a multi-variant phase change on cooling and a considerable amount of retained cubic phase. In range II, from 400 g per sq mm to the elastic limit, hexagonal regions of a given orientation grew in size and the cubic phase disappeared with increasing stress level. In range III, just above the elastic limit, specimens transformed into hexagonal single crystals. It was found that plastic deformation, not applied stress, was the factor which determined whether a single-crystal product was formed. The observed macroscopic shear directions were mainly (112) on cooling, but the behavior was more complicated on heating under stress. To explain these properties of the phase change, a model based on the nucleation of partial dislocations is proposed. IT is well-known1 that, on heating, hcp cobalt transforms into an fcc arrangement by shearing on close-packed planes. The crystallographic orientation relationship of the phases is as follows: the habit plane is (OOO1)hcp ?{lll}fcc and a (1010)hcp direction is parallel to a (112)fcc direction. The temperature at which the transformation occurs in pure cobalt is around 420.C 1,2This temperature decreases with increasing nickel concentration: and at about 30 pct Ni it reaches room temperature. However, many of the transformation characteristics remain essentially the same, particularly the crystallographic features.495 A convenient way of studying the transformation is to alloy cobalt with nickel, thus avoiding the difficulties of doing experiments at the high temperatures needed to transform pure cobalt. Due to the hysteresis of the transformation it is possible to choose a Co-Ni alloy with an Ms temperature below room temperature and an A, temperature above room temperature. Either structure of such an alloy could then be studied at room temperature, depending on whether it had just been heated or cooled to room temperature. The choice of nickel is further favored by the small difference in lattice parameters between cubic cobalt and nickel and the similarity of their physical, chemical, and electronic properties. Co-Ni alloys are reported to have neither long- nor short-range order.6 The main purpose of this work was to investigate the influence of an external stress on the transformation characteristics of Co-Ni single crystals. It may be expected that slip, twinning, and transformation should have many features in common in cobalt, because the (111) planes of the cubic phase operate as slip planes when plastic deformation by slip occurs, they are the twinning planes, and they are the habit planes for the transformation. Many previous investigators7-&apos;6 have concluded that dislocations must play an important role in the nucleation and propagation of the transformation, just as they do for slip and twinning propagation. An external stress will affect their motion, and a study of its influence should yield further information about the atomic mechanism of transformation. The present work extends that of Gaunt and christian17 and Nelson and Altstette18 in both qualitative and quantitative effects of stress. The basic concept underlying all the present theories of the transformation of cobalt and Co-Ni alloys is the motion of a/6<112> partial dislocations over {1ll} planes of the cubic lattice. The ABCABC... stacking of the close-packed planes of the cubic phase can be changed into the hexagonal ABABAB... stacking by the sweeping of an a/6 <112> partial on every second plane. Twinning, on the other hand, requires a shear of a/6 <112> on each close-packed plane. The reverse transformation can be effected in a similar way by a/3 (1010) dislocations moving over every other basal plane of the hexagonal phase. Transformation theories2, 7- 12,14 differ in the details of the nucleation of the transformation and the propagation of the partial dislocations from plane to plane. EXPERIMENTAL PROCEDURE Nickel and cobalt rods supplied as 99.999 pct pure were induct ion-melted together under a vacuum of about 10-5 torr in a 97 pct alumina crucible. An alloy containing 30.5 pct Ni was found to have the desired transformation range, with an Ms near -10°C and an j4s in the vicinity of +10O°C. The ingots were swaged to &--in. rod and electron beam zone-leveled in a 10-6 torr vacuum. This procedure resulted in 12-in.-long single fcc crystal rods (designated I to VII) from each of which several tensile specimens of identical orientation were made. Chemical analysis of the bar ends indicated no contamination or gross segregation and no micro segregation was seen in electron micro-probe scans. Tensile specimens with a 9/32-in.-sq by 1-in.-long gage section were spark-machined from the rods and then electropolished or chemically polished to remove the machining damage and to provide a flat surface

Jan 1, 1970

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol&apos;kenshtein&apos;s effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS&apos; attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1&apos; of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan&apos; investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0&apos;~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther&apos; investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By C. W. Binckley, F. R. Burgess, E. R. Haymaker

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By D. K. Das, P. A. Beck, S. P. Rideout

IN a previous publication1 1200°C isothermal phase diagram sections were given for the Cr-CO-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo ternary systems, in which the a phase formed narrow, elongated solid solution fields. The present investigation is concerned with the 1200°C isothermal sections of the Co-Ni-Mo, Co-Fe-Mo, and Ni-Fe-Mo ternary systems. A prominent feature of these systems is the presence of narrow, elongated µ phase fields. The crystal structure of the phase designated as µ both here and in the previous publication1 was determined by Arnfelt and Westgren.2 For the (CO, W)µ phase, named by them Co,W, (and also frequently designated as a), these authors found that the crystal system is hexagonal-rhombohedra1 and the space group is D53d — R3,. Westgren and Mag-neli3 later found that isomorphous phases exist in the Fe-W and the Fe-Mo systems (these phases are often referred to as < and E, respectively). Henglein and Kohsok4 stated that the phase described by them as Co7Mo,; (otherwise frequently designated as c) is also isomorphous with the above three. The Co-Fe-Mo system was investigated at 1300°C by Koester and Tonn,5 who found a continuous series of solid solutions between (Co, MO)µ and (Fe, MO)µ Koester6 also indicated similar uninterrupted solid solutions in the Ni-Fe-Mo system. However, since the Ni-Mo binary system does not have a phase isomorphous with F, Koester&apos;s diagram is expected to be erroneous. No data appear to be available in the literature concerning the Co-Ni-Mo system. The face-centered cubic (austenitic) solid solut,ions of iron, nickel, and cobalt, which are quite extensive in all three systems at 1200°C, are here designated as the a phase. The body-centered cubic (ferritic) solid solutions, based on iron, are designated in this report as the ? phase, in conformity with the nomenclature used previously.&apos; Experimental Procedure The alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. The lot analyses for the metals used have been given.&apos; The number of alloys prepared was 46 for the Co-Ni-Mo system, 65 for the Co-Fe-Mo system, and 113 for the Ni-Fe-Mo system. The compositions of these alloys were selected with due regard to maximum usefulness in locating phase boundaries. The alloy specimens were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting almost entirely of the face-centered cubic austenitic a phase, or of the body-centered cubic ferritic c phase were double-forged with intermediate annealing. The double-forged specimens were then final annealed for 90 hr at 1200 °C and quenched in cold water. Alloys containing considerable amounts of any of the other phases could not be forged. Such specimens were annealed for 150 hr at 1200°C and quenched. Microscopic specimens of all alloys were prepared by mechanical polishing, in many cases followed by electrolytic polishing. Description of the polishing and etching procedures used and tabulation of the intended compositions of the alloys prepared are being published in two N.A.C.A. Technical Notes.7,8 , Many of the alloys were analyzed chemically and, in general, the results are in excellent agreement with the intended compositions. X-ray diffraction samples were prepared by filing or crushing homogenized alloy specimens and by reannealing the obtained powders in evacuated and sealed quartz tubes. After annealing for 30 min at 1200°C the tubes were quenched into cold water. X-ray diffraction patterns were made with unfiltered chromium radiation at 30 kv, using an asymmetrical focusing camera of high dispersion. X-ray diffraction and microscopic methods were used jointly to identify the phases present in each specimen. The amounts of the phases in each alloy were estimated microscopically. The phase boundaries were located by the disappearing phase method. The results were used to construct 1200°C isothermal sections for the three ternary phase diagrams. The accuracy of the location of the phase boundaries determined in this manner is estimated to approximately ±1 pct of each component. The portion of the three phase diagrams lying between the µ, P, and 6 phases on the one hand, and the molybdenum corner on the other, has not been investigated. Recently Metcalfe reported0 a high temperature allotropic form of cobalt on the basis of dilatometric results and of cooling curves. In the present work no attempt was made to search for the new phase in the cobalt corner of the Co-Fe-Mo and Co-Ni-Mo systems. No alloy was prepared with more than 80 pct Co; the alloys used were intended to locate the boundary of the a phase saturated with cL. The microstructures of the quenched a alloys near the cobalt COrner gave no suggestion of an in-suppressible transformation On quenching. The location of the boundaries of the a + ? two-phase fields in the Fe-Ni-Mo and Fe-CO-MO systems was determined entirely by the microscopic method. The face-centered cubic a alloys near the ? field transform partially or wholly into the body-centered cubic ? phase on quenching from 1200°C to room temperature. The ? formed in this manner has an

Jan 1, 1953

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md&apos;ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,&apos;-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-&apos; Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.&apos;-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman&apos; have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By Shiou-Chuan Sun

THE fact that coals of different ranks and even of the same rank differ greatly in their amenability to iroth flotation is well known. In recognition of the need for an explanation of this phenomenon, two hypotheses have been suggested. Wilkinsl reported that the floatability of coals increased with an increase of the carbon content or rank. This postulate is handicapped by the fact that bituminous coals that possess moderate carbon contents are actually more floatable than anthracite coals that have high carbon contents, as shown in columns 6 and 9 of Table I. Taggart and his associates&apos; implied that the difference of floatability between bituminous and anthracite coal was caused by the variation of carbon-hydrogen ratio. This is not applicable to the relative floatability of other coals and carbons. For example, column 11 of Table I shows that the carbon-hydrogen ratios of low-floating lignitic coal and non-floating animal charcoal are not only smaller than the moderate-floating anthracite coal, but are also similar to the high-floating bituminous coal. Furthermore, according to this hypothesis, high temperature coke-A (464), Ceylon graphite (1238), and lamp-black (357), all possessing extremely high carbon-hydrogen ratios, should be less floatable than other substances having much lower carbon-hydrogen ratios such as high volatile-B bituminous coal (11.9 to 22), anthracite coal (35.7 to 60.5), lignitic coal (15.6 to 33.6), and charcoal (13 to 26.2). However the former group is actually more floatable than the latter group. In this paper, a surface components hypothesis is Proposed to explain the different floatabilities of coals, carbons, and hydrocarbon minerals. The validity of the hypothesis is experimentally supported by the actual floatability, natural floatability, wettability, and adsorbability for neutral oils of coals, carbons, and hydrocarbon minerals tested. The combustible recovery of the flotation results, as used in this paper. was calculated from Eq. 1: P (100-Ep) 100 RWCP Rc= [1] F (100-E,) C, where R, is the percent combustible recovery; F and P are, respectively, the weight of feed and the weight of concentrate or product; E, and Ep are, respectively, the total percent of ash plus moisture in feed and in concentrate; Ru. is the percent weight recovery: and C, and C, are, respectively, the percent of combustible in feed and in concentrate. Except for ash and moisture content, all chemical components of a coal are assumed combustible. The experimental work included studies on flotation, ultimate and proximate analyses, contact angle tests, extractions of bitumen-A with benzene, adsorptions for liquid hydrocarbons, and wetting tests. Most of the flotation experiments were performed in a laboratory Fagergren machine; others were tested in a small Denver machine. The solid feed for the former was 300 g and for the latter was 30 g. The solid materials used for flotation were crushed to —48 mesh. After the mineral pulp in the flotation cell was agitated for 6 min and the pH was adjusted to 7.5 & 0.2 with sodium hydroxide or hydrochloric acid, a petroleum light oil having a viscosity of 5.73 centipoises at 77 °F was added and conditioned for 2 min. Finally, pine oil was introduced and the froth was collected for exactly 3 min. The weight ratio of petroleum light oil to pine oil was kept constant at 1.5 to 1. Tap water was used for all flotation tests. Contact angles were measured with a captive bubble machine. For each coal sample, three specimens were mounted in transoptic mounts and polished with levigated alumina, first on a sheet glass, then on a cloth-covered metal polishing wheel. The polished specimen was first washed with distilled water and wiped thoroughly on a cleaned linen pad, then transferred into the pyrex cell of the captive bubble machine and conditioned for 6 min., and finally measured for contact angles at three or more points. Except where otherwise stated, the induction time for each measurement was 1 min. The contact angle representing each material was obtained by averaging the measurements of three specimens. The linen pad was first washed with warm distilled water, then boiled 30 min in a 2N sodium hydroxide solution, and finally washed with distilled water until no trace of sodium hydroxide could be detected in the decanted solution. The cleaned linen pad was stored under distilled water. Immediately before using, the pad was rewashed and transferred into a clean pyrex petri dish partly filled with distilled water. The glassware and rubber gloves used were cleaned by soaking in sulphuric acid-potassium dichromate cleaning solution, followed by rinsing with distilled water. The polished specimens were handled only by glass forceps. The ultimate and proximate analyses were made in accordance with the ASTM standard procedures for coal and coke. The extractable bitumen-A was determined by weighing 1 g of —100 mesh sample and placing it in a desiccated and weighed ASTM aluminum-extraction thimble. The thimble was placed in condenser hooks and inserted into an extraction flask containing 100 cu cm of benzene. The flask was heated and the benzene vapor was condensed by water coils. At the end of 24 hr of percolation, the thimble was removed, desiccated, and weighed. Loss in weight of sample was taken as bitumen-A and calculated to dry and ash-free basis.

Jan 1, 1955

By J. L. Tomlinson, B. D. Lichter

Electrical resistivities 01 liquid Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi alloys were measured using an electrodeless technique. The resistivities ranged from 50 to 160 microhm -cm, temperature dependences were positive, and no sharp peaks in the composition dependence of the resistivity were observed. On the basis of these observations, it was concluded that the alloys are typical metallic liquids. The electron con-cent9,ation was calculated from the measured resis-tizlity and available thermodynamic data using a model which attributes electrical resistivity to scattering by density and composition flzcctuations. A correla-tion was shown between the departure of the electron concentration from a linear combination of the pure component valences and the value of the excess integral molar free energy. Calculation of the temperature dependence of the electrical resistivity showed a need for more detailed thermodynamic data in these systems and led to suggestions for improvement in the concept of residual resistivity in the fluctuation scattering model. THE electrical resistivity of liquid metals provides information regarding interatomic interactions and their effects upon structure. In this experiment an electrodeless technique was used to measure the electrical resistivities of liquid alloys of Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi, and the results were used with thermodynamic data to calculate a parameter which reflects the tendency toward localization of electrons due to compositional ordering. It was found that the resistivities of these alloys are generally metallic in magnitude and temperature dependence. The electrical and thermodynamic properties are discussed in terms of the fluctuation scattering model&apos;22 which supposes that the electrical resistivity arises from scattering due to a static average structure and departures from the average due to fluctuations in density and composition. Further, this model is compared with the pseudopotential scattering model of Ziman et al.3-5 EXPERIMENTAL PROCEDURES Alloy samples were prepared from 99.999 pct pure elements obtained from American Smelting and Refining Company (except tin which was obtained from Consolidated Smelting and Refining Company.) J. L. TOMLINSON, Member AIME, formerly Research Assistant Division of Metallurgical Engineering, University of Washington, Seattle, Wash., is now Physicist, Naval Weapons Center, Corona Laboratories, Corona, Calif. 0. D. LICHTER, Member AIME, is Associate Professor of Materials Science, Department of Materials Science and Engineering, Vanderbilt University, Nashville, Tenn. This work is based on a portion of a thesis submitted by J. L. TOMLINSON to the University of Washington in partial fulfillment of the requirements for the Ph.D. in Metallurgy, 1967. Manuscript submitted May 31, 1968. EMD Weighed portions were sealed inside evacuated silica capsules, melted, and homogenized before the resistivity was measured. The resistivity of a liquid alloy was measured by placing the sample inside a solenoid and noting the change in Q. According to the method of Nyburg and ~ur~ess,~ the resistivity of a cylindrical sample may be determined from the change in resistance of a solenoid measured with a Q meter as T7--5--W =R7JT^ =&apos;Kc-lm(Y) [1] where L, R, and Q = wL/R are the inductance, series resistance, and Q of the solenoid. The subscript s refers to the solenoid with the sample inside; the subscript 0 refers to the empty solenoid. Kc is the ratio of the sample volume to coil volume and y = 2 [bei&apos;0(br)-j ber&apos;o(br)~\ br\_bero(br) +j bei0 (br) expressed with Kelvin functions which are the real and imaginary parts of Bessel functions of the first kind with arguments multiplied by (j)3&apos;2. The argument of the function Y is hr where r is the sample radius and b2 = po~/p, i.e., the permeability of free space times 271 times the frequency divided by the resistivity in rationalized MKS units. Since Eq. [I] cannot be solved explicitly for p, values of Kc. lm(Y) were tabulated at increments of 0.1 in the argument by. A measurement of Q, and Q, determined a value of Kc . lm (Y) and the corresponding value of br could be read from the table. From the known r, uo,, and w, the resistivity, p, was determined. The change in Q was measured after letting the encapsulated Sample reach equilibrium inside a copper wire solenoid. The solenoid was contained in an evacuated vycor tube in order to retard oxidation of the copper while operating at high temperatures and heated inside a 5-sec-tion nichrome tube furnace capable of obtaining 900°C. Temperature was determined with two chromel-alumel thermocouples, one in contact with the solenoid 30 mm above the top of the sample and the other inserted in an axial well at the other end of the solenoid and secured with cement so that the junction was 2 mm below the bottom of the sample. Temperature readings were taken with respect to an ice water bath junction, and the voltage could be estimated to the nearest thousandth of a millivolt. The lower thermocouple was calibrated by observing its voltage and the Q of the coil as the temperature passed through the melting points of samples of indium and tellurium. The upper thermocouple reading was systematically different from the lower thermocouple reflecting the temperature difference due to a displacement of 60 mm axially and 6 mm radially. Calculations show that the gradient over the sample was less than 2 deg. Q was measured by reading a voltage related to Q from a Boonton 260A Q meter with a Hewlett Packard

Jan 1, 1970

By W. S. Morris

THE East Texas oil field is the largest in the United States and perhaps the largest &apos;in the world ; likewise, it is one of the most interesting. The East Texas oil field is a water-drive field. Small amounts of salt water were produced from wells on the western side of the field from the bt-ginning of the development. By the end of 1933 (the field having been discovered in September 1930) water production had reached 9000 barrels per day. By the end of 1936, approximately 2000 wells were producing about 45,000 barrels of water per day, and the problem of salt water disposal attracted the serious attention of the operators. Salt water production in the field has steadily increased and today approximately 450,000 barrels of water per day is produced while the oil production averages about 375,000 barrels. The disposal of this salt water has therefore become one of the major operating problems. Various methods of salt water disposal have been tried in the East Texas field. Evaporation in open pits proved

Jan 1, 1944

By Allan J. Clark

THE September issue of MINING AND METALLURGY might almost have served as a review of the advances in the metallurgy of gold during the current year. In addition to a scholarly article by F. W. Bradley, there were able descriptions by W. W. Bradley and W. F. Boericke of the methods followed in California and in Ontario. Considered together, the two last-named articles indicate the many possible combinations of flotation with one or more of the older processes. This, the prominence of flotation as an aid in the beneficiation of gold ores, is probably the most striking of the year&apos;s developments. It would perhaps be nearer the fact to say that the year has not been marked by the gold metallurgists&apos; discovery of the flotation process, but rather by the flotation merchandizers&apos; discovery of gold metallurgy. I say this because native gold was floated successfully more than fifteen years ago, and a reference to these results was published six years ago.

Jan 1, 1933

By Arthur Connolly

WHEN scientific literature was lacking or meager, research necessarily meant laboratory investigation above all else. Today, scientific literature has attained tremendous proportions, and the volume increases at a much faster rate than it is digested and efficiently utilized. For that reason the present-day research worker should spend much more time in the library, and correspondingly less in the laboratory, than is the general custom. Library research would overcome two serious errors often made by scientists: duplication of work described completely and failure to appreciate inventions described almost verbatim in the literature. To emphasize these failings that often occur in present-day research, consider a hypothetical scientist as he conducts his search from inception to the stage where it is made available to the public by patent or other publication.

Jan 1, 1942

By R. W. Raymond

FOUR portraits have recently been hung in the rooms of the Institute, in recognition of four illustrious men with whom we, as mining engineers and metallurgists, may claim fellowship. LUTHER. Martin Luther is often spoken of as a miner&apos;s son; but it is less generally known that John Luther, his father, was, in a small way, a metallurgist as well as a miner, and that Martin Luther himself, in his youth, worked in a forge or bloomary established by his father at Mansfeld, Saxony. Since this is the only manual occupation on his part of which we have any record, it is fair to assume that the great scholar and reformer derived from his work in this department the practical familiarity with the conditions of human labor so abundantly evinced in the homely illustrations which accompany even his serious arguments, and in the witty apothegms of his famous "table-talk." At the same time, I must confess that 1 have not been able to find in any of the works of Luther distinct allusions to mining or metallurgy. KÖRNER. Theodor Körner, a student at the Mining Academy of Freiberg, Saxony, threw himself into the German War of Freedom in the first decade of the 19th Century. He was a poet of no mean rank ; and his " Song of the Sword " is one of the great lyrics of literature. This poem was written but a few days before he died in battle. In many respects, Körner may be compared with our American hero Theodore Winthrop, who similarly met a glorious fate, and left behind him prophetic indications of genius, of which his premature death prevented the complete fulfillment. I am informed by a member of the Institute that Körner&apos;s admirable collection of minerals is still preserved at Dresden.

Nov 1, 1908