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By Marcel R. Daly

The writer has devoted a number of years to practical operations and to the study of geology in the oil fields. In consequence, he has been brought to investigate the theories advanced to account for the accumulation of oil and gas in commercial deposits. It is the result of these investigations and his personal conclusions that he wishes to sum up in this paper. The writer is an advocate of the organic origin of petroleum found in pools. He has been led to believe that the present theories of oil and gas accumulations are incomplete and, in certain respects, incorrect, although they may embody certain elements of truth; that the forces that are called upon to explain the movement are only secondary forces in the process, and insufficient, by themselves, to cause this movement; and that the phenomenon of accumulation is of much larger order than heretofore admitted and bears an intimate relation with the general as well as with the local deformations of the crust and is a direct consequence and a mechanical effect of these deformations to which the term " diastrophie " has been applied. As a complement to this theory, the writer offers a new interpretation of the "rock pressure" and of the mechanism of the "sealing up" of this pressure in oil and gas pools. The Anticlinal Theory The theory most generally accepted to account for the accumulation of hydrocarbons in commercial deposits is the anticlinal or structural theory. This theory, the principles of which have been laid down by I. C. White, Orton, Winehell and others, and which has since been modified and perfected, is too well known to need a detailed statement. A clear interpretation of it may be found, in the paper of W. T. Griswold, in Bulletin No. 318 of the United States Geological Survey, and the reader is

Jan 1, 1917

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS t ARE ASSOCIATES THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION HEAVY FACED TYPE SIGNIFIES HONORARY MEMBERSHIP ` *AARONS, JULIAN B , Mine Supt, The Boulder Deep Levels, Ltd , Boulder, Western Australia, '05 *ABADIE, EMILE R, Cons and Min Engr, 1004 James Flood Bldg, San Francisco, Cal '76 *ABBE, CLEVELAND, JR, GeOl Aid, U S Geological Survey, Washington, D C '00 *ABBOTT, AI ARTHUR, Cerro de Pasco Mining CO , Cerro de Pasco, Peru, So America '95 *ABBOTT, ARTHUR V , Electrical Engr , Westinghouse, Church, Kerr & CO , 8 Bridge St, New York, N Y '82 *ABBOTT, CLARENCE E, Chief Min Engr, Care Fayal Mine, Eveleth, Minn '04

Jan 1, 1910

By Ernest F. Burchard

The Pao deposits of iron ore are in the State of Bolivar, Venezuela, near Upata, about 30 miles south of the Orinoco River and 90 miles east of Ciudad Bolivar. They were discovered 4 or 5 years ago and have not yet been developed to the stage of mining. In March-April, 1929, the writer devoted a week to the examination of these deposits. The maps, drill records and chemical analyses presented herewith were derived from original sources, and the field photographs were made by the writer. The petrographic and metallographic data are from notes by C. S. Ross and M. N. Short, of the U. S. Geological Survey, who have kindly collaborated in these special phases of the study. The Iron Obebodies Topography and Accessibility The deposits are in a region of low mountains representing northern outliers of the Guayanan Highlands. These mountains reach altitudes of 1800 to more than 2000 ft. above sea level, as determined by aneroid barometer. The iron ore is found on mountain crests that reach altitudes of 1915 to 1930 ft., and may be followed down precipitous slopes for 200 • to 300 ft. or more. The greatest vertical range in outcrop is nearly 400 ft., and drilling has indicated that the ore extends to this depth below the surface in one place, at least. The superior hardness of the iron ore accounts for the preservation of the local mountain crests with the intermediate valleys eroded in softer granitic rock. The deposits of iron ore are reached by a private road for automobiles branching northeast from the Ciudad Bolivar-Upata road, a distance of about 12 miles. This road was used in 1928-29 by trucks for transportation of food and camp supplies, gasoline, drilling equipment, etc., but was not suitable for the transportation of iron ore. Between Ciudad Bolivar and the iron-ore area the western two-thirds of the automobile road passes through nearly level, open country known as the savanna, largely used for grazing cattle. About 96 km. (60 miles) east of Ciudad Bolivar at

Jan 1, 1931

By Harlowe Hardinge

[Crushing Tests by Pressure and Impact (T.P. 1895, by F. C. BOND,, Min. Tech. Jan. 1946). Discussion by H. HARDINGE and the author 1 Pumping Sands, Slurries and Slimes and Installation and Performance of Sand Pumps (T.P. 2013, by W. B. STEPHENSON, Min. Tech., May 1946 and T.P. 1978, by C. G. SOUTHMAYD, Min. Tech., March 1946). Discussion by OSCAR LEE, G. J. HOLT, L. D. ANDERSON, and the author 2 Rapid Polarographic Method for Determination of Copper, Zinc and Lead in Flotation Tailings (T.P. 2010, by G. A. CROWE and W. T. BISHOP, Min. Tech., March 1946). Discussion by E. H. ROSE and the authors 4 Ball Wear and Functioning of the Ball Load in a Fine-grinding Ball Mill (T.P. 1984, by W. I. GARMS and J. L. STEVENS, Min. Tech., March 1946). Discussion by J. F. MYERS, E. W. DAVIS, F. M. JARDINE, H. HARDINGE, F. C. BOND and the authors 5 Correlation between Mineral Behavior in Cataphoresis and Flotation (T.P. 2005, by A. M. GAUDIN and S. C. SuN, Min. Tech., May 1946). Discussion by 0. C. RALSTON, G. L. SIMARD and D. J. SALLEY 7 Accident Experience in Milling (T.P. 1981, by J. F. MYERS and S. E. SHARP, Min. Tech., May 1946). Discussion by C. E. MCKNIGHT, C. H. BENEDICT, T. S. WILSON and S. POWER WARREN9 Mill Design for Labor Economy (T.P. 1997, by NORMAN WEISS, Min. Tech., May 1946). Discussion by R. S. HANDY and the author13] Crushing Tests by Pressure and Impact (0.C. Ralston presiding) HARLOWE HARDINGE.*-Has the impact method described in the paper been used to compare the resistance to reduction in size of various materials with actual operation results of mills in the field? Is this impact method a better index of the true resistance to grinding under actual field conditions than other methods the author has reported in the TRANSACTIONS? F. C. BOND (author's reply).-The impact crushing device was designed to measure relative resistance to crushing, or what may be called the crushability, and is not used for comparing the resistance to grinding, or grindability. The correlation between crushability and grindability of different materials is not at all close, since fractures, zones of weakness, and structural features of rock have a much greater effect upon the crushability than upon the grindability. We still depend upon our standard grindability tests for measuring resistance to grinding, and use the impact crushing tests only in relation to crusher installations. The impact crushing device has several advantages over the measurement of crushing strength in pounds per square inch as an index of crushing resistance.

Jan 1, 1946

By Thomas O. Ziebold, Robert E. Ogilvie

Experimental analysis of diffusion samples covering the entire Cu-Ag-Au system at 725°C has been carried out. Experimental coefficients are computed at twenty-eight points in the lermary system. It is found that the direct coefficienl for copper is nearly independent of the silver, content for 1ow-silver alloys and that the cross coefficient for silver correlates with the ther-nzodynatnic properlies. This lalter observalion leads to the conclusion that the mobililies of copper and gold are nearly equal. Thermodynarmic actiuilies for Cu-Ag-Au were computed from binary data and adjusted to be consistent with neasured tie lines across the two-phase region which extends into the ternary diagram at 725°C. Application of these therknodynarnic calculaliorls to the dijftcsion data terifies the Onsager reciprocal relations to the extent that experimental uncertainlies will allow. It is jound that diffusion neav the critical point of the 1200-phase field in the isothermal section at 725°C causes the composition gradients for copper and silver to approach infinity while the direct and cross coeficients become equal. From the standpoint of experimental Procedures, it has been shown that microanalysis of ternary samples may be carried out using a simple expression for the conversion of X-ray zntensily to composilion. The accuracy of' this method has been demonstrated by the analysis of standard alloys and by the reproducibility of composition determinations using differed X-ray lines. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. When only two elements are present there is just one independent composition variable, and the diffusion profile of composition vs distance across a sample must change monotonically through all solid solutions bracketed by the terminal alloys. If two-phase regions are stable for compositions between the terminal values, these must appear as planar interfaces in the diffused sample, with the composition profile exhibiting sharp discontinuities. Adding a third element may alter this picture completely. Because of the additional degree of freedom in the composition, we may see composition profiles which do not change monotonically through solid-solution ranges, and stable, nonplanar phase interfaces. Even though two-phase regions may lie between the terminal compositions of a diffusion sample on the constitution diagram, they will not necessarily appear in the diffusion profiles. In binary diffusion only one coefficient is needed to describe the interdiffusion process. From Fick's law this coefficient relates the diffusive flux of one component to its own composition gradient. In ternary diffusion we must allow for cross interaction between the two independent species. By a linear extension of Fick's law we introduce "cross" or "off-diagonal" diffusion coefficients which relate the flux of one component to the composition gradient of the other independent constituent. Thus, we require four interdiffusion coefficients to describe the transport process in a ternary system. In its most general form,1,2 the rate equation for mass transport by isothermal diffusion in a system of s components states that the diffusive flux of component i, Ji, is a linear summation of all driving forces, Xk, each force being multiplied by an appropriate compliance coefficient:

Jan 1, 1968

By W. J. Rude

LARGEST of the known commercial deposits of pebble phosphate are those found in Polk County, Florida. The phosphate bed, commonly known as the matrix, will consistently average 6 to 9 ft. in depth, and is found under 3 to 60 ft. of over-burden. The phosphate pebbles, white and black in color, varying greatly in grade, are found imbedded in a matrix of sand and clay; and range in size from the fines to pebbles 1 1/2 in. in diameter, although the average coarse size is approximately 1/2 in. in diam¬eter. On some of the washers all material under 14 mesh is lost. High-grade phosphate (75 per cent plus of bone phosphate of lime, CasP2Oa) is generally soft, the pebbles breaking up during the mining operation and in pumping; low-grade phosphate, 67 to 69 B.P.L., is black in color with hard pebbles with no loss encountered in pumping.

Jan 1, 1941

By AIME AIME

ON Thursday, Oct. 9, oil men from far and wide gathered at Beaumont, Texas to participate in a three-day celebration of the fortieth anniversary of the completion of the famous Lucas gusher well at Spindletop field just south of Beaumont, and to pay tribute to Anthony F. Lucas, for whom the Lucas Medal of the A.I.M.E. is named. In the afternoon the gathered host drove to the site of the discovery well to dedicate a 58-ft. granite monu¬ment erected on the spot where the original derrick stood. Representatives of the A.I.M.E. took a prominent part in the dedication ceremonies, giving the two principal addresses of the afternoon's program. Everette DeGolyer, past President, paid a personal tribute to Capt. Lucas, as a pioneer producer, an engineer, and a friend and well wisher of all young engineers. He gave a splendid picture of the useful and full life of Capt. Lucas who always took a great interest in the activities of the Petroleum Division of the Institute, from its inception to the time of his death.

Jan 1, 1941

BASIC open-hearth slags have no obviously unique features when compared with slags from other metallurgical operations. Open-hearth slags form and exist at temperatures ranging from 2500 to 3100 F (1370 to 1700 C). In the course of an open-hearth heat, the liquid slag changes slowly and continuously in chemical analysis-the changes reflecting changes in temperature, changes in metal analysis, solution of charged materials, solution of feed additions, and solution of refractories. Through- out the process, the slag performs specific primary functions that are responsible for a large measure of the technical and economic importance of basic open-hearth steelmaking. It is intended in this chapter to present the chemical reactions by which the primary functions of basic open-hearth slags are carried out, to describe the physical and chemical principles governing the extent to which these reactions proceed and can be regulated, and finally to indicate the limitations imposed on other features of the process by the fulfillment of the primary functions. Basic open-hearth slags perform three primary functions. First and foremost, the slag provides a means of removing phosphorus from the liquid metal. The ability to remove phosphorus is largely responsible for the widespread use of the basic open- hearth process. Second, the slag serves as a controlling factor in transferring the oxygen required for the other oxidizing reactions. Third, the slag provides a means of eliminating some sulfur from the open-hearth bath. While the extent of sulfur removal is not comparable to that of phosphorus, the ability to remove some sulfur contributes much to the value of the process. The effectiveness with which the slag fulfills its functions varies with temperature and composition. Since operating temperatures are fixed largely by the specified nature of the product and the equipment, the speed and extent to which the functions of the slag are carried out depend largely on its composition. The necessity for regulating slag composition to accomplish the re-

Jan 1, 1951

By Norman P. Goss

What would appear to be a very simple process on paper has proved to be overrun with a multitude of unseen difficulties. For more than 70 years attempts have been made to cast metals in a continuous manner, but it has been only within the last Io years that some degree of success has been achieved.1 Historical Development Bessemer's Experiments—Method I Bessemer was the first to try to cast molten metal in a continuous manner. His method is fully described in U. S. Patent No. 49053, issued in 1865. The patent drawing is shown in Fig. I. In this method the molten metal was poured between a pair of rolls of large diameter, which were cooled by water sprays. Means were provided to prevent moisture from coming into direct coptact with the molten metal. The width of the strip was controlled by the flanges. On paper this should work to perfection, but it is beset with many difficulties still awaiting solution. Bessemer failed to reduce his invention to commercial practice. About 1890 Bessemer's method was revived by Norton and associates (U. S. Patent No. 441375). They formed the Fluid Metal Rolling Co. at Maywood, Ill., and spent $250,000 in endeavoring to develop the technique for this simple method. Finally they had to abandon it. Naturally, they did carry the technical development far beyond anything Bessemer had done, but even so it was far from being a useful commercial success. In recent years it has undergone further development by C. W. Hazelett (U. S. Patent No. 2058447), who has succeeded in obtaining long lengths of copper, brass, aluminum, and even stainless steel. He introduced many' ingenious devices but the greatest obstacle still remained—the disintegration of the roll surface when the surface is heated and chilled in rapid succession. Difficulty is also experienced in maintaining a uniform supply of molten metal to the rolls. The patents pertaining to this method would indicate these to be the major obstacles. Experimental work by Mellen—Method 2 A departure from the method introduced by Bessemer, was tried by Grenville Mellen, of East Orange, K. J., sometime between 1914 and 1920, who obtained a number of patents.2 His method is illustrated in Fig. 2. This method failed to make an impression upon the art; however, it is of value in pointing out the difficulties the inventor ran into and the way in which he tried to meet them. The split mold sections form two endless chains. When going through the center of the apparatus, these sections engage each other to form a complete mold. As the engaged mold section moves downward at a constant speed, molten metal is teemed into it. As this is going on, another set of cooperating mold sections move into position on top of the one being filled. The molten metal is teemed into the mold through a silica tube. According to the teachings of this patent, the level of molten

Jan 1, 1945

By O. D. Sherby

In 1938, Kanter' revealed that the steady-state creep rate of low-carbon iron alloys could be correlated by an activation energy expression, where the activation energy for creep, Qc, was found equal to about 90.0 kcal per mole for most of the alloys investigated. He suggested that creep at high temperatures might be controlled by some sort of solid self-diffusion process since the value of Qc was about equal to the known value for self-diffusion, Qd. Correlations were not further attempted along these lines until many years later, when new evidence2-8 was presented suggesting that Qc = Qd for many metals. This equality now appears to be established for ten metals (Al, Pb, Ni, Mg, Cd, In, a Fe, y Fe, Cu, and Au). This experimental fact prompted several investigators to postulate various mechanisms of dislocation motion which would yield an activation energy for creep equal to that for self-diffusion.7-9 Possibly the most accepted theory is that based on dislocation climb7 where a dislocation is envisioned to surmount a barrier by an atom-vacancy exchange process, thereby "climbing" from one slip plane to another. Such a model would suggest that the steady-state creep rate, i, should be directly proportional to the rate of self-diffusion, D, for a given creep stress. In order to more clearly reveal the relationship between creep and diffusion, and to eventually determine the correct model, it would be desirable to obtain data showing correlations between i and D, rather than with a comparison of the temperature coefficients, Q. It has been known for some time that the self-diffusivity of iron atoms is greatly decreased when body-centered-cubic (a) iron transforms to face-centered-cubic (y) iron. This has been ascribed to the more close-packed structure of y iron. The diffusivity ratio at the transition temperature is Da/Dy =350. Correlations of creep data for a and y iron5 reveal that the creep rates under a given stress at the transition temperature differ by about the same ratio (ea/ey 2 200). It would be difficult to reconcile these results on any other basis than that the diffusivity of atoms probably controls creep of iron in some very direct way. No other published data on other allotropic metals appear currently available for further checking such a possible correlation between i and D. Thallium transforms from a hexagonal close-packed (a) structure to a body-centered-cubic (ß) structure at 230°C (503°K) and the self-diffusivities of the two structures have been determined by shirn.10 His results are plotted in Fig. 1 where it will be noted that Dß/Da = 25 at the transition temperature. It would appear desirable, therefore, to determine the creep rates of polycrystalline a and ß thallium at the transition temperature, as well as determine

Jan 1, 1959

By W. W. Yankie, A. T. Chatas

This paper is written as a discussion of the paper, "Buckling of Tubing in Pumping Wells, Its Effects and Means for Controlling It" by Arthur Lubinski and K. A. Blenkarn, which war published in the March, 1957, issue of Journal oP Petroleum Technology. An analogy is drawn between the buckling of tubing in pumping wells and a fiube, fitted with frictionless pistom, linked by an inelastic rod, and which is subject to an internal pressure. A simple derivation shows that the critical internal pressure exerts a hydrostatic force on the pisfon which is close to the Euler load for compression buckling of the same tube. While the results agree with those of Ref. I, the basis of calculations has been changed and clarified. The presence of internal upsets at the pistons is discussed. INTRODUCTION In the Appendix, Lubinski and Blenkarn state that a tube with ends closed by frietionless pistons connected by an inelastic rod (Fig. 1) will behave as a column loaded with a force equal to the tension force in the rod. They note that, while the fluid may not resist a shear force, the moment in every cross section is piston force multiplied by the elastic line deflection (c.f., the loaded column). Since the equations of the elastic lines are similar in the two cases, the solution is carried over from the loaded column. On the contrary it is suggested that while the method of solution remains unchanged from the column case, the actual stress distribution is different, a fact which is taken into account in this note. A simple method of approximating the buckling pressure is given, and their reasoning in our mathematical language is continued. GENERAL EQUATIONS The equation of an elastic line, initially straight in the x direction (Fig. 2), is given by In the case of a loaded column, this may be written: For the pressurized tube it was shown, by analogy with the loaded column, that tion has a solution that, for P, = EI/P, any deflection is stable (a criterion for buckling). An attempt will be made to describe more precisely, the forces acting on the tube, and to analyze the buckling condi,tions. DISCUSSION If the tube assumed a deflected position, the volume between the pistons would increase so that in deflecting, the energy of the fluid would decrease. When the increase in elastic energy of the tube (due to bending) is equal to the decrease of fluid pressure energy, buckling conditions exist. Analyzing the forces on the tube (Fig. 3), two transverse forces, T,, T,, exerted by the pistons, are balanced by a resultant of the pressure elements which are linearly dependent on the local curvature of the elastic line (Fig. 4). Unlike most buckling cases, the forces depend on the shape of the elastic line, a condition that makes a rigorous mathematical treatment difficult. Several approximations may be used to clarify the problem.

By J. E. Burke

RECENT investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen, Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: [D=Ktn [11] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Walker4 finds that, in alpha brass, the rate of growth falls off more rapidly than indicated by Eq I after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: [t, Hr i '_ III t„ = R \T, - ~) [2]] where t1 and t2 are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck.' The results obtained by Beck, Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and Hu6 later demonstrated experimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,10 Making implicit use of this assumption, several authors14,15 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parker' have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary, are on the average more surrounded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1948

By S. J. Rothman, J. J. Hines, D. Rokop, R. Bastar

Self-diffusion has been measured along each principal axis of mosaic-structured and relatively perfect a uvaniuln single crystals. The anisotropy reported before,' D[loo] = D[001] » D[010 , has been confirmed. and is shown to represent volume diffusion. Diffusion along the dislocations in the imperfect crystals increases the measured value of D significantly without changingr either the shapes of the penetvation plots or the anisotropy. SINCE a uranium is orthorhombic, the diffusion coefficients along the principal crystallographic axes need not be equal. A previous measurement of self-diffusion in three mosaic-structured a uranium single crystals1 showed that Dil00| =D[001 >>D[010 This result was deduced from penetration plots similar to those in Fig. 1. That is, the plots for diffusion along [loo] and [001] were the straight lines expected from the solution of the diffusion equation for the boundary and initial conditions of the experiment, while the plot for diffusion along [010] was curved so that the part near X = 0 had a much steeper slope than the straight lines did. The observed anisotropy could have been due either to volume diffusion or to diffusion along the very large number of dislocations in such crystals, according to the model proposed by aart.' The authors of Ref. 1 argued that the latter possibility was unlikely, but did not exclude it. To settle the question, a simultaneous measurement of self-diffusion in mosaic-structured and mosaic-free crystals was carried out. This paper reports the results, as well as a measurement of the temperature dependence of self-diffusion in a uranium. EXPERIMENTAL The single crystals of a uranium used in this experiment are listed in Table I, together with other experimental details. '(Mosaic structured" here means crystals grown by solid-state phase change.3 The Laue spots from such crystals spread over about 6 deg of arc, which indicates that the density of dislocations is very large. "Perfect" crystals are ones grown by Fisher's grain-coarsening tehnique; the Laue spots from these are quite sharp,4 which shows that the dislocation density in these crystals is much lower. All of the crystals were made from high-purity uranium; a typical analysis is given in Ref. 1. The actual diffusion directions were within a few degrees of the nominal. The thin layer-sectioning method was used. The experimental techniques were similar to those described in Ref. 1, except the sectioning. Crystals Za, 2b, 2c, 4a, 4b, and 4c were sectioned on a lathe. Crystals 3a, 3b, and 3c were sectioned by grinding on glass plates, with 1 p diamond powder in butyl alcohol as the abrasive. The use of glass plates eliminated the crowning noted in Ref. 1, and the use of butyl alcohol as a lubricant simplified the chemical processing of the sections. Material from the sides of these three crystals was removed by spark machining before sectioning. The sectioning of crystals 4a and 4c was botched. A small cylinder of metal was extruded from the center of crystal 4a while turning off material from the side of the sample. Crystal 4c was misaligned by 2.1 x 10"3 cm because the dial gage jammed during the alignment. Notwithstanding these errors, useful data were still obtained from these crystals. The points

Jan 1, 1967

By C. H. Fulton

Page Introduction........................... 280 Distillation Products from Reduction of Zinc Ore........... 281 Preliminary Investigations..................... 290 Equilibrium of Reaction Zn + CO2 + ZnO + CO in Temperature Range of Condensation........................ 293 Requisites for Successful Condensation................ 299 Discussion............................ 300 Introduction The study of the condensation of zinc from its vapor was undertaken to shed light on certain problems encountered in large-scale electric zine-furnace work. recently conducted. It is a matter of common knowledge that one of the disadvantages of the arc type, electric zinc furnace, is the production of a large amount of blue powder and proportionately little liquid spelter, for, as stated by Stansfield,l "A notable defect in the electric smelting of zinc ores is the difficulty experienced in obtaining the distilled zinc in the liquid state; ...... when zinc ores are smelted electrically, very little liquid metal is commonly obtained, nearly all of the zinc being in the state of powder." This difficulty was not encountered in the electric furnace used12 the main difficulty being the destruction of the fire-brick lining of the large condenser, in certain parts, and the formation of .some oxide and dross coatings on the condensing surfaces. The reason for these difficulties could readily be explained by the infiltration of air whenever the condenser was changed from one retort base to the other, the zinc absorbed in the fire-brick forming oxide and causing rupture by its expending volume. Two facts, however, tended to disprove this theory for the rupture of the fire-brick lining: first, the large distilling retort, lined with fire-brick, which was shifted from charge to charge on alternate bases at temperatures between 1200 and 1300 C., fully exposed to the air, showed no signs of disintegration whatever; second, marked disintegration in the condenser occurred .only in places that were at tempera-

Jan 1, 1919

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The addition of nitrogen (0.10 to 0.20 pct) to Fe-Cr-Ni alloys of simulated commercial purity results in a real displacement of the u phase boundaries to higher chromium contents. The effect is small for the (Y + s)? boundary, but is pronounced for the (y + a +s)/(y + a) boundary. Although there is an indication of an exceptionally large shift of the n boundaries to higher chromium contents, especially in steels with nitrogen over 0.2 pct, the major portion of this apparent shift results from the fact that carbide and nitride precipitation cause "chromium impoverishment" of the matrices. The effect of combined additions of nitrogen and silicon to the Fe-Cr-Ni phase diagram is demonstrated also. Nitrogen can nullify the effect of about 1 pct Si in shifting the (y + o)/? phase boundary to lower values of chromium at all nickel levels from 8 to 20 pct. NItrogen can nullify this U-forming effect of about 2 pct Si at the 8 pct Ni level, but not at the 20 pct Ni level. The alloys studied were in both the cast and the wrought conditions. There are indications that the u phase forms more slowly in the cast alloys than in the wrought alloys if both are in the completely austenitic state. The presence of 6 ferrite in the cast alloys accelerates the formation of U. Cold working increases the rate of o formation in both cast and wrought alloys. THE major improvement in Fe-Cr-Ni austenitic alloys in recent years has been in the addition or removal of minor alloying elements to facilitate better control of corrosion resistance, sensitization, and heat resistance. One shortcoming of the austenitic Fe-Cr-Ni alloys, which never has been completely circumvented, is their propensity toward u formation. In the AISI-type 310 (25 pct Cr-20 pct Ni) and type 309 (25 pct Cr-12 pct Ni) steels, sufficient amounts of u phase can form, if service or treatment is in a suitable temperature range, to cause severe embrittlement. Also, there is a growing conviction that this phase may be contributory to some unexpected decreases in the corrosion resistance of certain of the 18 pct Cr-8 pct Ni-type steels. The present paper discusses the effect of nitrogen additions on the location of the (r+u)/d and the (y+a+u)/(y+a) phase boundaries in the ternary Fe-Cr-Ni system, for cast and wrought alloys of simulated commercial purity, and in similar alloys containing up to about 2.5 pct Si. The objective is to define compositional limits for alloys which will not be susceptible to u formation when used near 1200°F (650°C). An excellent review of the early studies of the u phase in the Fe-Cr-Ni system has been compiled by Foley.1 Rees, Burns, and Cook2 have determined a high purity phase diagram for the ternary system, whereas Nicholson, Samans, and Shortsleeve3 are- stricted themselves to a portion of the simulated commercial-purity phase diagram. Both groups of investigators show almost an identical position for the commercially significant (y+u)/y phase boundary. Further comparison of the work of the two groups indicates that, below the 8 pct Ni level, the commercial alloys have a decidedly greater propensity toward u formation than the high purity alloys. The two groups of workers agreed that both the AISI-type 310 (25 pct Cr-20 pct Ni) and the type 309 (25 pct Cr-12 pct Ni) steels are well within the (y+~) region and that the 18 pct Cr-8 pct Ni-type alloys straddle the U-forming phase boundaries. Nicholson et al.3 showed, in addition, that these boundaries shift toward lower chromium contents if greater than nominal amounts of silicon or molybdenum are added. The effect of nitrogen on the location of the s phase boundaries in the Fe-Cr-Ni system has not been known with any certainty. In 1942, an approach to this problem was made by Krainer and Leoville-Nowak,' but at that time they apparently were unaware of the slow rate of s formation in strain-free samples and aged their samples for insufficient times, e.g., 100 hr at 650°C (1200°F) and 800°C (1470°F). For this reason, it would be expected that their (y+ u) /y boundary would be shifted toward lower chromium contents (restricted ?-field) when equilibrium conditions were approximated more closely. Procedure for Studying the Alloys The alloys used were prepared in the following way: Heats of 200 lb each were melted in an induction furnace. A 5 lb portion of each heat was poured into a ladle containing an aluminum slug for de-

Jan 1, 1955

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By H. I. Aaronson, C. Wells

Configurations of ferrite crystals have been found in a plain carbon steel which appear to have resulted from the nucleation of new ferrite crystals at the interphase boundaries of previously formed crystals despite the high carbon concentrations which necessarily develop at these boundaries. This phenomenon has been termed sympathetic nucleation. An attempt has been made to reconcile the occurrence of sympathetic nu-cleation with current nucleation theory. THIS investigation is one of a series on the formation of proeutectoid ferrite from austenite. From the viewpoint of chemical composition, this reaction consists of the nucleation and diffusional growth of crystals of carbon-poor ferrite within a matrix of carbon-rich austenite. The austenite adjacent to the austenite-ferrite boundaries will be greatly enriched in carbon, approximately to the value of the y/(a + y) equilibrium curve or its metastable extrapolation at the temperature of transformation. Those areas of austenite appreciably farther removed from the growing ferrite, on the other hand, will be relatively unaltered in composition, especially at the earlier stages of transformation. Since rates of nucleation are considered to decrease exponentially with decreasing supersaturation,' the frequency with which ferrite nuclei appear at austenite-ferrite boundaries should be negligible in relation to that at which they form in other regions of the austenite. During this investigation, however, many groupings of ferrite crystals have been found which appear to have resulted from the nucleation of ferrite at austenite-ferrite boundaries. This phenomenon has been given the name of sympathetic 71.1tcleation. A number of micrographs of morphological configurations caused by sympathetic nucleation will be presented, after which an explanation for this reaction will be proposed in terms of current nucleation theory. Some of the structures to be considered are composed of bainite, an aggregate of ferrite and carbide, rather than of ferrite. Since ferrite and bainite differ only in that bainite forms under conditions which result in the nucleation of carbides behind the advancing austenite-ferrite boundaries,' it will usually be unnecessary, for the purpose of this paper, to distinguish between the two reaction products. All studies were performed on an electric furnace steel (obtained from the Vanadium Alloy Steel Co.) containing 0.29 pct C, 0.76 pct Mn, 0.25 pct Si, 0.005 pct P, and 0.007 pct S. The alloy was cast as a 150 Ib, 7x7 in. cross section ingot and forged into bars 2x2 in. in cross section. These bars were homogenized for 48 hr at 1250°C in an Endo-Gas atmosphere. The depth to which decarburization penetrated during this heat treatment was determined by chemical and microscopic analyses and the affected metal was removed by machining. Specimens for isothermal transformation studies were cut from the remaining material; most of these specimens were 1/2x1/4X1/16 in., though some with a thickness of 1/32 in. were prepared for use at the shorter reaction times and lower reaction temperatures. Specimens were austenitized for 30 min at 1300°C, isothermally reacted for various times at temperatures ranging from 775" to 475 "C, and then quenched in iced water. The austenite grain sizes within individual specimens ranged from ASTM Nos. 1 through —4. A commercial heat-treating salt which was continuously deoxidized by an immersed graphite crucible served to minimize the loss of carbon during austenitizing; thick covers of powdered graphite and immersed graphite rods effectively prevented decarburization in the lead pots employed for the isothermal reaction treatments. The heat-treated specimens were sectioned and mounted in Bakelite. Following the completion of standard grinding and mechanical polishing procedures, the specimens were electrolytically polished with a Buehler-Waisman apparatus and etched in 2 pct nital. Experimental Results Rules of Evidence for Sympathetic Nucleation—On the basis of observations made on a single plane of polish, one precipitate crystal may be considered to have been sympathetically nucleated at the inter-phase boundary of another precipitate crystal when the following conditions are fulfilled: 1) The sympathetically nucleated crystal is not in contact with a grain boundary or a subboundary in the matrix phase. 2) The shape, size, and location of the crystal at whose boundary sympathetic nucleation occurred (hereafter termed the base crystal) and the crystal formed by sympathetic nucleation substantially pre-clude the possibility that the plane of polish em-ployed may have concealed the fact that both crys-tals actually nucleated at a grain boundary or a sub-boundary in the matrix phase.

Jan 1, 1957

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941