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By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,' in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By E. H. Edwards, J. Washburn

Zinc crystals were deformed in simple shear and it was found that anisotropic strain hardening occurred in which the inactive slip systems were hardened more than the active system. The formation of dislocation barriers by dislocation interaction was discussed as a possible explanation of the hardening of the latent systems. STRAIN hardening which accompanies slip in a metal crystal is not limited to the slip systems actively contributing to the plastic strain. There is also a strengthening of the latent slip systems which are crystallographically equivalent to the active system. In the case of aluminum deformed in tension, Taylor and Elam1 found that plastic flow on one set of octahedral planes caused either the same or a slightly greater hardening on an inactive set. Similar results have been obtained for crystals of a brass2 and of Cu-A1 solid solutions.3 Experiments by Rohm and Kochendorfer4 indicated that the hardening of the active system exceeded the hardening of any latent system for aluminum crystals deformed in shear. On the other hand, strain hardening in zinc and cadmium crystals tested in simple shear at —196°C was recently found to be greater in the latent than in the active slip direction." When the strain direction was shifted during testing to a direction 60" from the original, a higher stress was required for glide to continue than would have been needed for flow to proceed in the original direction. The relation between the hardening of active and latent systems must be complex, depending upon the relative orientations of the systems and upon the experimental techniques used to deform the crystal. A detailed knowledge of the hardening produced in latent systems would be valuable in choosing between possible dislocation models of the strain-hardening process. The experimental data now available are incomplete and even contradictory. The present study was undertaken to provide quantitative information regarding the relative amount of hardening of active and latent systems for a particularly simple case. Zinc crystals were deformed in simple shear along one of the three crystallographically equivalent directions [250], [1210], and [1120] in the slip plane, and the relative hardening produced in each of these directions was compared. Experimental Procedure and Results The single crystals of 99.99 pct purity zinc used in this investigation were grown from the melt in the form of 1 in. diam spheres. Shear specimens were acid-machined from the crystals by a method which has been described previously. The gage section of the test specimen was a cylinder having a height of 1/8 in. and a cross-sectional area of approximately 1/3 sq in. All specimens were machined with the axis of this cylindrical gage section aligned with the [0001] axis of the crystal. An innovation in the design of the shearing apparatus for these tests was the provision for a rapid shift in the direction of the applied stress from one slip direction to any other slip direction lying in the same slip plane. Fig. 1 shows a section through the specimen and shearing apparatus, and Fig. 2 is a

Jan 1, 1955

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

By K. B. Nowels

DATA pertaining to pipe line flow for both oil and gas in horizontal or nearly horizontal pipe lines are both extensive and accurate. However, the pipe formulas used to determine pressure drop for flowing fluids (liquids and gases) under conditions of horizontal flow are not generally applicable to flowing oil and/or gas wells. Except for some data developed in small laboratory set-ups, little or no information was available concerning flow of oil and gas mixtures in vertical pipes, when, in 1928, the writer began the development of a method for computing pressure drops in the pipes of flowing oil wells, as outlined in this paper. In 1929, Uren1 presented some findings based on laboratory experi-ments in which vertical flow of an extremely heavy crude oil was induced, by means of air through a 2-in. pipe, 41 ft. long. The friction factors derived from the experiment, as well as values for pressure drop per 100 ft., are not believed satisfactory in their application to flow problems in the field. Versluys,2 also in 1929, presented a mathematical development of the theory of flowing oil wells, and in 1930, gave a companion paper3 setting forth some principles governing the choice of length and diameter of tubing in oil wells. Since the termination of the study presented in this paper, another. valuable contribution pertaining to the problem, of vertical flow was made by Moore and Wilde.4 Although there were writings dealing with the principles of the gas-lift, a search of the available literature indicated that specific information on vertical flow was lacking with the exception of the writings of Uren, Versluys, and Moore and Wilde, to which reference .has been made.

Jan 1, 1932

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder's equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By Raymond C. Boettner

The present work had for its purpose: 1) the identification of crack nucleation sites in AISI 4340, quenched to martensite and tempered over a range of 'temperatures; and 2) the comparison of fatigue processes in AISI 4340 with processes observed previously in pure metals From constant def1ection-bending fatigue tests, martensite boundaries were identified as the favored crack nucleation sites in quenched and tempered AISI 4340. It, also, was concluded that the fatigue processes operating- in this lous-alloy steel were similar to Processes observed in pure tnetals. ALTHOUGH much engineering data has been accumulated on the fatigue properties of quenched and tempered martensitic steels,' fatigue as a process is not as well understood in martensite as it is in pure metals.' Important features of the fatigue process, such as the identity of the nucleation sites, have not been determined in the commercially important high-strength low-alloy structural steels. The present work had for its purpose: 1) the identification of crack nucleation sites in a low-alloy steel, i.e., AISI 4340, which had been quenched to martensite and tempered over a range of temperatures; and 2) the comparison of fatigue processes in the AISI 4340 with processes observed previously in pure metals. This comparison of the fatigue processes in the different tempers was restricted to the high-strain low-cycle part of the S-N curve. Under these test conditions, previous work on a number of metals has shown that a large number of cracks are nucleated in less than 30 pct of the fatigue life.3 Furthermore, crack nucleation sites are not restricted to inclusions but are also associated with intrinsic structural characteristics of the metal. MATERIAL A 20-lb ingot of vacuum-melted AISI 4340 (for composition see Table I) was hot-rolled to 1-in.-diam rod and then cold-rolled to a 1-in.-wide strip, 0.08 in. thick. Fatigue specimens, see insert of Fig. 1, were machined from the strip with the long dimension parallel to the rolling direction. m this orientation, the stringers of 1 to 2 p inclusions present in the sheet lay parallel to the stress axis in the specimens. The specimens were austenitited at 2050°F in order to obtain a large prior austenite grain size, i.e., 2 mm, which facilitated the subsequent identification of the prior austenite boundaries. A helium atmosphere was used to minimize decarburization. After austenitiza-tion at 2050°F, the specimens were transferred to a 1450°F furnace so that specimen distortion was held to a minimum in the subsequent oil quench. Previous work4 indicated that refrigeration in liquid nitrogen prior to tempering reduced the percentage of retained austenite in the quenched specimens to less than 5 pct. Tempering was carried out in air over the temperature interval of 200°to 800°F to produce a range of mechanical properties, Table I. The preparation of the fatigue specimen was completed by grinding about 0.005 in. from each surface and electropolishing in a chrome trioxide-acetic acid solution for 30 min. Examination of etched cross sections of specimens prepared in this fashion showed the foregoing specimen preparation to be adequate for the removal of the decarburized layer present after the heat treatment. Transmission electron microscopy showed that the as-quenched microstructure of this alloy consisted of a mixture of martensite plates containing either a high density of dislocations or microtwins. Previous work5'6 indicated that in the course of oil quenching autotem-pering resulted in the formation of E carbide on the martensite and microtwin boundaries. Tempering for 2 hr at temperatures up to about 400°F resulted in further precipitation of the E carbide. Finally, at about 400°F, cementite began to replace the E carbide on the martensite and microtwin boundaries in addition to forming a Widmanstatten structure within the plate matrix. EXPERIMENTAL S-N curves were obtained using electropolished specimens cycled at 1800 cpm as cantilever beams in fully reversed bending at selected constant deflections. The deflections were translated into surface strains by means of a calibration curve obtained through the use of strain gages. An argon atmosphere was used to minimize environmental effects. To investigate the development of fatigue slip bands, the specimens of the different tempers were unidirec-tionally bent to a surface strain of 0.005 to 0.007, photographed to record the location and appearance of slip bands so introduced, and then cycled to failure

Jan 1, 1968

By James F. Kemp

In submitting an additional contribution to the discussion on ore-deposits in the recent volumes of the Transactions, it is my desire to adhere closely to matters of material importance as affecting the actual processes. Judging from the discussion by Professor Van Hise, and from one or two reviews or other articles by associates of his in geological work, the impression seems to prevail that, in so far as my paper* referred to his masterly essay, I was guilty of misconceptions regarding both the part attributed by him in it to the igneous rocks and the ubiquitous presence of the ground-water. I should regret extremely to be wanting in these particulars or to have misunderstood one for whose great services in this and other branches of geology no one has a higher esteem than myself. I have, however, in the most careful way, and with these points in mind, read his essay again, and, taking it as a whole, I cannot gain any different impression of relative magnitudes than the one first received. The importance of the igneous phenomena and the restrictive influence of the processes described by " cementation " in their effect upon the ground-water, as set forth in Professor Van Hise's "Discussion" (Trans., xxxi., 292), impress me as being in very marked contrast with the same things in his first essay. If the point seems to anyone of sufficient importance, it can easily be decided by reading the originals. My paper was the result of some years of observation, reading and reflection, and was meant to be an independent contribution, controversial only in some subordinate particulars. In depicting the drama of the deposition of ores, I cannot but feel that Professor Van Hise assigned to the chorus and the scene-shifters some characters which, it seems to me, should

Jan 1, 1903

By J. J. Jakosky

A REVIEW of the progress in applied geophysics during the recent depression years reveals marked advances over the methods employed several years ago. Of late, geophysical work has been curtailed to a Con-siderable extent in the fields of oil and base-metal exploration, its especial domains a few years ago. Greater attention has been directed toward the use of geophysical technique in other engineering problems. Constantly maintained research programs have developed new instruments and per-fected better field, laboratory and interpretation techniques based on experience and skill acquired from years of application in the older geophysical field. During the past two years, geophysical methods have been employed in problems that required information on thickness of fill materials and subsurface bedrock contours. Considerable success has been attained, with subsequent drilling checking the predicted depths within one to five per cent. In general, these problems were similar as far as the fundamen-tal physical and geological conditions were concerned, but they have varied widely in specific detail and in engineering aspects. Character-istic of the different problems are: (1) yardage and bedrock profile in gold-placer mining; (2) water supply, involving underground drainage and storage conditions; (3) bedrock contours in dam-site and other structural investigations; (4) gravel and fill yardage, and other structural features along rights of way and in rock and gravel quarrying. Of particular interest, perhaps, to mining men are the problems of gold placer deposits and water supply. Geophysical work on gold placers is of especial interest because of the present expanded activity in all phases of gold mining. The development of a suitable water supply at an economical cost is often of prime importance in insuring a successful mining venture. Particularly is this true in the arid Southwest. How-ever, the use of geophysical work in water supply is not confined to the needs of mining development.

Jan 1, 1933

By C. van Dijk

In Sept., 1960, a steam-drive project was started in the solution-gas drive area of the Schoonebeek field. A part(ern of three five-spots and one four-spot was selected covering an area of 65 acres. The pay in the project area has good lateral continuity and dips slightly to the northeut; it is about SO ft thick and permeability increases from 1,000 and at the bottom to approximately 10,000 md at the top. The oil originally in place was 12.6 X 10' bbl. The oil has an in situ viscosity of about 180 cp. At the start of the steam drive the cumulative primary production due to. solution-ga.7 drive amounted id 4 Percent of the oil originally in place. Reservoir pressure had dropped about 120 psi and no significant primary re-.serves remained. Some 11.3 million bbl of steam (all steam quantities are expressed in barrels of water vaporized) have been injected, resulting in production of an additional 4.1 X I0 9bl of oil, or 33 percent of the oil originally in place. This corresponds to a cumulative oil-stearn rario of 0.37 bbllbbl. It appears that the steam preferentially moves r updip while liquids are produced mainly from downdip wells observations indicate that tile steam flows through only the upper part of the formation. The lateral steam distribution in the pattern is satisfacrory since several prodriction wells hardly reacted and, hence, cori tributcd little to the oil production. Production performance and results from material balance calcutlations agree satisfactorily with the results of large-,scale laboratory experiments. On the basis of these experirmental results the .steam drive, together with a cold water follow-up. is expected to bring ultimate recovery to a value of crt leas: 50 percent of the oil originally in place. No serious production problems have been encountered. However, due to mechanical fuilure, two old prodriction wells and one injection well had to be replaced. An extension of the. steam drive in this area is under connstruction. Introduction The Schoonebeek oil field, discovered in 1943 and developed after World War 11, is situated in the eastern part of the Netherlands. The main oil reservoir in this field is the Valanginian sand. A completely sealing fault divides this reservoir into two areas (Fig. 1): the southwestern part of the sand body where primary production is ob- tained by means of a solution-gas drive, and the remain. der where edge-water drive is the production mechanism. In the greater part of the field the reservoir consists of a single, unconsolidated sand body. The net thickness ranges from 30 to 100 ft and the top is between 2,400 and 2,800 ft below sea level. Formation permeability varies from approximately 10,000 md at the top to values of the order of 1,000 md at the bottom, and porosity is about 30 percent. The reservoir contains a paraffinic oil of 25" API gravity with an in situ viscosity of 160 to 180 cp. Initial oil saturation was high (85 to 90 percent). The relatively large quantity of oil in place (more than 10' bbl), and the low ultimate primary recoveries expected from this field — approximately 15 percent stock-tank oil initially in place (STOIIP) for the water-drive area and 5 percent STOIIP for the solution-gas drive area — clearly indicate ample scope for secondary recovery. Because ies-ervoir and crude characteristics made this field suitable for thermal secondary recovery, a hot-water drive project was started in the water-drive area about 10 years ago. A few years later a steam drive and an in situ combustion project were started in the solution-gas drive area. This paper deals with the performance of the steam-drive project, which was started in Sept., 1960, and which is still in operation. Design of Steam-Drive Project, An experimental investigation of the steam-drive process carried out by schenk in 19561 indicated that under schoonebeek conditions steam injection could be an attractive secondary recovery method. the findings and encouraging results of a pilot test in the Mene Grande field in venezuela,i led to the design of a steam-drive project in the schoonebeek field, Pruject Site and Pattern In 1958 the reservoir pressure in the solution-gas drive area had decreased to about 120 psi, and oil production rates of wells in this area had dropped to 7 to 10 B/D. The cumulative primary production was about 4 percent STOIIP, leaving an oil saturation of approximately 85 percent. In view of the large amount of oil left behind in the reservoir, the solution-gas drive area was selected for the planned steam-drive project. The area in the vicinity of Well S1 3 (Fig. 2) was considered to be suitable since it is at least partly isolated from the rest of the field by faults and the sand is relatively thick (about 80 ft).

Jan 1, 1969

By Robert Mehl

IT has been shown that quenched iron of high purity exhibits a Widmanstätten figure much resembling martensite in appearance.1 This figure exhibits a maximum of four directions of the surface traces that characterize it, suggesting that a Fe forms from y Fe in plates parallel to the {111}, octahedral, planes in the y lattice. Because of this, and also because of the general similarity to the structural appearance of martensite and to the Widmanstätten figure obtaining in slowly cooled hypoeutectoid steels it has been suggested2 that the orientation relation-ships obtaining between the y and a phases in pure iron are identical with those demonstrated in martensite3 and in slowly cooled hypoeutectoid steels,4 and indeed that the crystallographic mechanism of formation of a Fe from y Fe is the basic mechanism determining the orientation relation-ships found in both martensite and in slowly cooled hypoeutectoid steels. This paper will present experimental evidence in support of this view.

Jan 1, 1934

EDMUND NEWTON, Minneapolis, Minn. (communication to the Secretary?).-In discussing the question of the deoxidation of steel and material suitable for performing this function at the end of the heat, it would seem logical also to include the question of prevention of oxidation in the steel or the formation of iron oxide, FeO. I refer to the use of manganese in the basic open-hearth and basic Bessemer processes. The advantages of high manganese in pig iron for these processes have evidently been clearly understood in Germany for a number of years, although little has been written in regard to the exact manner in which the benefits are obtained. In this country, while we make no steel by the basic Bessemer process, our basic open-hearth process is becoming more and more important. Until 10 years ago, in this country, manganese in the pig iron for this process was considered of little value and by many writers it was spoken of as a disadvantage. During the past 10 years, however, in certain parts of the United States, higher contents of manganese in basic pig have been used with considerable success, although there is apparently nothing in our technical literature to show the reasons for this trend. A German book, "The Basic Open-Hearth Steel Process" by Carl Dichmann does, however, offer an explanation. Dichmann says that if the charge for either of the above-mentioned processes contains 3 per cent. of manganese or above, satisfactory steel.

Jan 6, 1917

By C. S. Matthews, H. C. Lefkovits

The purposes of this study are (a) to determine the accuracy of a previously proposed method for calclrlating average reservoir pressure and (b) to find a method for estimating the shape of the drainage area of each well in a bounded reservoir. Both numerical and experimental methods are used to determine the pressure distribution and the location of drainage bounrlaries in idealized reservoirs at steady state. A number of photographs are included which show flowlines and drainage areas in reservoir models of various shapes. Results from these studies are then compared with those from the previously proposed method for calculating average reservoir pressure.' It is concluded that the previously proposed method is sufficiently accurate for most reservoir engineering purposes. In addition, some simple methods are given for estimation of .shapes of drainage boundaries. INTRODUCTION A method for the determination of the average Pressure in a bounded reservoir was previously developed by Matthews, Brons, and Hazebroek,1 and presented at the Petroleum Branch Fall Meeting in 1953.† In aP- plying this method, the reservoir was first divided into drainage volumes; second, the average pressure in each drainage volume was calculated; and third, these drainage volume pressures were averaged volumetrically to give the average pressure in the reservoir. It was shown that each well's individual drainage volume, at steady state, is proportional to the well's production rate; however. the question of how to estimate accurately the shape of these drainage volumes could not be answered. Furthermore, in calculating the average pressure for each drainage area, the actual drainage areas, which are in general quite asymmetric in shape, are replaced with one of the symmetric prototypes given in T.P. 3876. A question may then be raised as to how accurately the symmetrical figures depict the pressure behavior of the actual unsymmetrical drainage areas. The study reported on in the present paper was made in an attempt to shed light on the above questions. METHODS It was shown in T.P. 3876 that after a period of steady rate of withdrawal the rate of pressure decline becomes constant at every point in a bounded reservoir containing a single-phase fluid whose compressibility is small and constant and whose viscosity is con-

Jan 1, 1956

By J. R. Cain

In every process for making steel there are one or more stages where the metal is exposed to gas of one kind or another. Thus, in the open-hearth furnace, the carbon dioxide and water vapor in the products of combustion are oxidizing toward the ferrous and manganous oxides in the slag, tending to convert these to higher oxides; the higher oxides then , oxidize the steel, so that indirectly the products of combustion are oxidizing toward the steel. In the Bessemer process, there is direct contact of air and steel; also, the water vapor in the air blown into the converter is continually decomposed by the molten steel, yielding hydrogen and ferrous oxide, both of which are in part taken up by the metal. In the electric-furnace processes, there is always more or less air in contact with the slag covering the metal, and this air and the gaseous reaction products from it are dissolved in the slag to some extent and thus transmitted in part to the steel. In the crucible processes, there is always entrapped air in the charges and the crucibles are more or less permeable to the gaseous products of combustion from the furnace. In all the processes of manufacture, the molten metal is exposed to air while tapping into ladles and ingot molds and has an opportunity to saturate itself with air or with gaseous or solid products generated by chemical reactions between air and steel. Sievertsl has shown that molten metals requirc but a few seconds to saturate themselves with a surrounding gas. No one familiar with the operations at a steel plant needs to be reminded of the important role that gases play at all stages. The familiar "boil" of open-hearth furnaces, due to evolution of carbon monoxide when iron ore is added to the molten steel; the spectacular operation of the Bessemer converter brought about entirely by a gaseous reagent; the almost magic effect of small quantities of silicon, manganese, or aluminum added to the molten metal in ladle or furnace in quickly preventing bubbling and evolution of gases; the unwelcome phenomena of blowholes in ingots that have not been properly manufactured—these

Jan 1, 1920

By Y. C. Liu, R. H. Richman

From rolling textures of polycrystalline AgCl determined as a function of temperature, changes in the amounts of the individual textural components are correlated with temperature-dependent changes in glide geometry. The preferred orientations are influenced by the slip behavior as follows: 1) pencil glide, characterized by (110) slip directions and a greater participation in the deformation the higher the temperature, leads to a(012) fiber texture; 2) low-temperature deformation, primarily on (110) (110) systems, generates the {237}-(11, 9, 7) component; and 3) slip on {111}(110), comprising a significant portion of the room-temperature deformation, generates the {135}(211) and {110}(112) components. Typical re crystallization textures are also presented and briefly discussed. SPECIFIC relations between flow mechanisms in crystals and the individual orientations or components in deformation textures are necessary for a thorough understanding of the origin of such textures. Within each ordinary class of crystal struc- tures there is insufficient variety in the observed preferred orientations to permit direct and unambiguous correlation between flow mechanism and texture. A second approach to this problem is the correlation of textural changes with some known variation in glide geometry within one substance,1 In this paper, the latter approach is applied directly to a material in which there are distinct changes in the character of glide with changes in temperature. Silver chloride, although a nonmetal, is reported to exhibit slip,2,3 fiber textures,4 and rolling textures5,6 crystallographically similar to those of the well-studied fcc metals;7,8 in addition, there is a marked temperature sensitivity of the glide planes upon which flow occurs.3 Previous investigations of textures in AgCl unfortunately did not employ methods sufficiently sensitive to define possibly important minor components in the texture, nor did they utilize the temperature dependence of the glide systems. Thus, in order to clarify the effects of changes in slip mechanism, this paper reports a survey, using semiquantitative methods, of preferred orientations in rolled AgC1. Inasmuch as the influence of prior deformation texture upon preferred orientations after annealing is also of interest, some representative annealing textures are presented.

Jan 1, 1965

By H. W. Johnson

DURING part of the year 1932, conditions at the plant of the Inland Steel Co. made possible the collection of data on two of the variables of blast-furnace operation, between which we observed an interesting correlation. The variation in percentage of coke ash in the coke seemed to be reflected in the variations in percentage of silicon and sulfur present in the iron. This subject is of particular interest during this period of low production because of its effect on quality and cost of pig iron. The consumers of pig iron are now more exacting in their requirements. Formerly 0.050 per cent sulfur was considered satisfactory; now many foundries and steel plants insist on iron under 0.030 per cent sulfur and expect it to average 0.025 per cent sulfur. To attempt to produce iron so low in sulfur and still have reasonably good furnace operation means that everything possible must be done to minimize all variations. This subject is also directly connected with the cost of producing iron. A blast furnace operates most economically and efficiently in rather narrow limits and so any variable that has range enough to disturb regular operation must be moderated. The importance of regularity is accepted and the methods followed to eliminate variations in materials such as coke and iron ore are recognized as indispensable. Uniformity of Ore and Variations in Coke Ash The delivering of uniform cargoes of well mixed ore to the blast furnace involves much handling and expense, but it is accepted that the trouble and expenditure are justified. After the ore reaches the dock, further mixing is assured by spreading ore in thin layers, preventing segregation by keeping piles level, variations in digging, and the use of several bins for one ore. And finally, the fact that the furnace burden generally contains three or more ores, together with several miscellaneous materials, eliminates the possibility of ill effects due to variations in any one. Thus, much effort is made to insure a uniform ore. But a variation in the percentage of silicon in ore is less detrimental than a variation in the percentage of ash in coke. The former affects

Jan 1, 1933

By E. W. Edson, F. W. Hertal

In some fields the problem of mud fluid is simple and easy of solution. But in the Ventura Avenue field the acquisition and disposal of good drilling mud is not the least of the problems that confront the operator. In fact, mud fluid in the Ventura Avenue field is a very important factor in the drilling of the wells. It is quite probable that many of the factors affecting mud in this field will not be found in most of the fields with which the reader is familiar. However, in the fields where the mud fluid causes no apparent problem it is probable that some of the points brought out in this paper could be used to economic advantage. In fields where caving and squeezing formations and high gas pressures are present, as in the Ventura Avenue field, it is believed that application of methods outlined will be of great assistance in drilling wells. On account of the sandy nature of the formation and the lack of suitable shale bodies in the strata drilled through in the Ventura Avenue field, the wells make practically no mud during drilling. It is necessary therefore to supply drilling mud to the wells that will carry the drill cuttings to the surface, and also will " wall up" the drill hole and prevent the sandy formations from caving. Mixing and Handling Mud Fluid The clay used to make the mud fluid is obtained from a shale stratum in the upper Pico (Plioccne) formation found about a mile on either side of the field. Since high gas pressures and caving formations were first encountered in the Ventura Avenue field and mud fluid was needed to combat them, the mixing of this mud fluid has gone through a process of evolution. First, the clay was mined and hauled to the derrick, where it was shoveled into the well and left for the churning action of the bit to mix into a mud in the hole. The next move was the construction of a mixer to mix the clay to a mud fluid which was pumped into the well. These mixing

Jan 1, 1930

By J. William Fehnel

The health hazard due to the inhalation of certain dusts in the mining industry has been recognized, but was not subject to state or federal inquiry in the United States until about 1916. Reports on miners' phthisis and associated effect of dust inhalation were published as early as 1903 in South Africa and in 1906 in Australia. A report was made by Lanzal in January 1917 of a study of 433 cases of miners' consumption among zinc miners in southwestern Missouri. In a preliminary report issued in 1915 Lanza and Higgins2 concluded that, while there were general causes, such as housing and working conditions, that tended to produce a high incidence of tuberculosis, the flint dust constituted an unusual element of danger, to which it was reasonable to attribute the unusual prevalence of tuberculosis. Later a clinic established under the joint sponsorship of the United States Bureau of Mines, the mine owners, and the Metropolitan Life Insurance Co. carried on an extensive study covering a period of five years. The results of this study have borne out the conclusions reached in the earlier surveys. The early surveys in this country indicated the necessity of determining the extent of the dust pollution of air associated with the various mining operations. The first determinations were reported on the weight basis, undoubtedly to make comparisons with work previously done in Australia. Later studies of dust in industry led to the development of more refined methods of sampling and enumeration on the basis of count in place of weight, so that by 1919 Knowles3 reported 53 methods.

Jan 1, 1937

By J. G. Thompson

OXYGEN, nitrogen and hydrogen are present in practically all metals in one or more of the following forms: (1) molecular gas in blowholes or blisters, (2) combined in nonmetallic inclusions such as nitrides, oxides or silicates, and (3) in solid solution in the metal. Gaseous elements, in some of these forms, are encountered in practically all metals and alloys but possibly have received most publicity in connection with iron and steel. In fact, the entire steel industry depends upon the control of the oxygen content during the refining process, as well as in the finished material, and it was only after the adoption of the use of efficient deoxidizers such as manganese that the production of good steel with a low carbon content became possible. In normally clean, sound steel the amount of hydrogen is negligible and the amounts of oxygen and nitrogen vary from a few thousandths to a few hundredths per cent. However, many of the effects attributed(27,31,40.41,53,54,55,56,62) ? to the presence of these elements are important and at first glance appear to be out of proportion to the amounts of impurities involved. The presence of oxygen is believed to affect the solubility of carbon in austenite and ferrite and thereby to affect the structure of the iron or steel. Such properties as strength, hardness, ductility, elastic limit, impact resistance, magnetic permeability, tendency toward caustic embrittlement, irregularity in carburization, the cutting life of tools, certain corrosion phenomena, the presence of flakes, seams, bands, ghost lines and hair cracks, and the tendency to age-harden, all have been attributed to the presence of oxygen.

Jan 1, 1932