Search Documents

By George W. Sears

In preparing this symposium, our ambition was to elicit authoritative expression of opinion concerning important selected phases of the industry from men active in it. Responses to requests for contributions were gratifying, especially so in view of the short time available. The generous and cooperative spirit of the industry as a whole is amply evident. Responses were received from the following, who are therefore the true authors of the paper: W. G. Adamson, General Manager of the pershin; Quicksilver Co., Lovelock, Nev.; Dudley Baird, Vice President, Pacific Foundry Co., San Francisco; Walter W. Bradley, State Mineralogist of California; W. D. Burcham, General Manager of the Brewster Quicksilver Consolidated, Terlingua, Tex.; William Forstner, San Francisco; H. W. Gould, of H. W. Gould & Co., San Francisco; Marcus Hulings, General Manager of the Chisos Mining Co., Terlingua, Tex.; Frank J. Katz, Chief Engineer, Division Mineral Statistics, United States Bureau of Mines, Washington, D. C.; Lloyd J. Lathrap, Superintendent, Nevada Quicksilver Mines, Inc., Lovelock, Nev.; W. R. Moorehead, General Manager, New Idria Quicksilver Mings, Inc., Idria, Calif.; F. W. Oakes, Jr., Terlingua, Tex.; C. N. Schuette, San Francisco. Brief Economic History of Quicksilver in the United States Quicksilver ore was first discovered in the United States at what was later the New Almaden mine in California, in the year 1824. Production also began here, but not until 1850, when it was stimulated by the active demand caused by gold-mining operations. Prospecting for quicksilver was active, high-grade ores were found and ample production lowered the price from $100 per flask in 1850 to about half that figure for the greater part of the next 10 years. During the succeeding decade, many new quicksilver mines were found; production increased at a time when the local demand diminished, so that most of the product was exported. The third decade of quicksilver mining in the United States witnessed the development of the pan amalgamation process, particularly in Com-stock silver-mining operations. A suddenly increased demand sent prices soaring, the all-time peak of quicksilver production followed, and the highest price was soon replaced by the lowest one on record. Huge quantities of quicksilver were exported between 1870 and 1880 and exports continued in decreasing measure for three decades to 1910. In

Jan 1, 1930

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By W. B. Triplett, H. I. Aaronson, G. M. Andes

A detailed morphological study has been made of the pro-eutectoid TiCr, and the eutectoid reactions in a Ti-17.42 pct Cr alloy isothermally transformed at temperatures from 775° through 5561°C. The morphologies of proeute,ctoid TiCr2 were found to be subject to description by the Dube morphological classification system. Grain boundary allotriomo.lphs are the dominant plpoeutectoid morphology throughout the temperature range investigated. lntragranular plates, and especially Widmanstatten sideplates, form only in small numbers. This morphological pattern differs markedly from that of the proeutectoid a reaction in hypoeutectoid Ti-Cr alloys (AIME Trans., 1957, vol. 209, p. 1227; 1958, vol. 212, p. 624), in which plates form prolifically throughout wide ranges of temperature. The eutectoid reaction is nonlamellar in character at 675°C. An increasingly prominent lamellar component develops at lower temperatures. The proeutectoid TiCr 2 and the eutectoid transformations have been studied metallographically in a hypereutectoid titanium-chromium alloy. This investigation was undertaken with the immediate objective of comparing these transformations with their counterparts in hypoeutectoid titanium-chromium alloys, studies of which have been recently completed.1,2 It was also intended, however, to contribute to the general literature on transformations of these types. Especially in the proeutectoid case, this literature is still sufficiently sparse to make difficult the testing of generalizations on the mechanisms of these transformations. TiCr, is the only intermetallic compound in the titanium-chromium system.3-5 The TiCr2 phase field extends to a maximum temperature of 1350°C) and encompasses the approximate composition range of 62 to 68 pct Cr at lower temperatures.3'4 At temperatures below 1000°C, TiCr2 has a MgCu,-type fcc structure, with 24 atoms comprising a unit cell.6,7 Only fragmentary observations on the morphology of proeutectoid TiCr2 have been previously reported. An observation which is of considerable importance with respect to the results obtained during the present investigation was made, however, on anisother-mally transformed alloys with high chromium (48 to 70 pct Cr) contents.3"8 Despite the occurrence of extensive impingement, it is apparent that a substantial proportion of the proeutectoid TiCr, which precipitated in these alloys grew in the form of Widmanstatten plates. Several observations have been made on the eutectoid reaction in hypereutectoid alloys during investigations of the titanium-chromium phase di-

Jan 1, 1961

By W. H. Hough, P. B. Leavenworth

Development in the upper Texas Gulf Coast during 1944 resulted in the discovery of 19 new fields as compared with 11 during 1943. These discoveries include 10 oil fields, one dry gas field, and eight gas-condensate fields. Drilling During the year 590 wells were drilled as compared with 418 drilled during 1943. Of these operations, 485 wells were drilled in proven fields, with the following results: 281 oil wells, 22 condensate wells, one dry gas well and 141 dry holes. The remaining 105 wells were wildcats, of which 19 were producers. The geological distribution of these discoveries was as follows: In 1944, production amounted to 178,-522,630 bbl., which was an increase of some 31,670,384 bbl. over the 1943 figure of 136,852,246 bbl. These figures include both condensate and oil production, as separate figures are not available. Wildcatting in the area was more successful during 1944 than in 1943 as the following comparison of number of wells drilled illustrates: Discoveries during 1944 Smith Point, Chambers County.—Standard Oil Company of Texas completed its No. I State, sec. 109, on Feb. 15, 1944, in a Frio sand at 8135 to 8146 ft. The well flowed 250 bbl. of 42º gravity oil through an 1/8-in, choke. Gas-oil ratio was 800 to I; tubing pressure, 1100 bbl. Four other oil wells and one gas well were completed during the year. This discovery does not appear to be of major importance. The producing area lies on the upthrown side of a large fault. North Winnie, Chambers County.—Sun Oil Co. completed No. I P. E. Dougherty on Apr. 27, 1944, from the Frio, through perforations at 8757 to 8759 ft. The initial production was 154 bbl. of 38.3º gravity oil through an 1/8-in. choke. Gas-oil ratio Was 2526 to 1; tubillg Pressure, 2280 1b.; casing Pressure, 1225 lb.; total depth, 9519 ft. Three other wells were drilled during the Year. This discovery is on the downthrown side of the major Winnie Stowell fault, and increases in magnitude the already large producing area along this fault. Mayes Field, Chambers County.—Humble Oil and Refining Company's No. I Mary Etta Mayes was completed on Dec. 24, 1944, in a Frio sand, at 8166 to 8169 ft. through 1/4-in. for 768 bbl. of 40.3º gravity

Jan 1, 1945

By R. J. Bethancourt, D. M. Collingwood

The use: of a pilot waterflood is very desirable where all of the pertinent data necessary to initiate a full scale waterflood are not. available. This paper attempts to take a specific case and .show the step by step process of starting with a pilot waterflood and progressing to a full wale flood as results are obtained. INTRODUCTION Many of the older fields of Soutlwest Texas are approaching depletion by primary produrtion methods. As primary protlllc:inp operations on individual properties approach their economic limit. conflicting considerations face management: cm the one hand. plugging and abandonment of wells for equipment salvage; on the other hand, further investment in secondary recovery installtions, equilent, and well workovers in the interests of conservation anal additional oil reserves. In main instances, where primary production by pressure depletion and gas solution drive has been comparatively good, there still exists the possibility of an economic secondary recovery by waterflood. This is not necessarily true to the same degrre of all such fields. nor all portions of large fields. To properly evaluate the economics of a prospective water-11ot1cI requires a considerable amount of precise geological. statitical. and physical data Such information on the older field.; is often very limited. and in the case of the property discussed in this paper was considered inadequate to justify investment in an overall waterflood. Primary production was estimated at :39 per cent of the original oil in place, yet sand conditions of permeability and homogeneity, and position in the field appeared to be favorable for a limited margin of profit from a carefully controlled waterflood. Thus a pilot waterflood, with its minimum initial financial risk, followed by extension as favorable results were obtained, seemed to be the answer for the Sun Oil Co L. Wiederkehr lease in the Nortl Government Wells Field, Duval County. Texas DESCRIPTION OF RESERVOIR Approxinately 8,200 wells have been drilled in Duval County. As of March 1, 1952, there were 3,350 producing oil wells in 92 different fields, with very few flowing wells (Fig. 1.) Sun Oil Co. operates the I.. Wiederkehr lease located in the North Government Wells Field in Duval Countv. 85 mile. west of Corpus Chriti and 100 miles south of San Antonio. The lease has been subjected in part to a controlled five spot waterflood. The North Government Wells Field is roughly 7 miles long and 3 miles wide, with numerous overlapping producing zones. The L. Wiederkehr lease of 3.085 acres. Has seven producing zones from 700 to 7.500 ft. The lease is in the northern section of the field where it is widest, and has 710 acres productive from the North Government Wells .and. (Fig. 2.) The North Government Wells sand, Jackson group. Eocene age, at an average depth of 2.250 ft (minus 1.750 subsea). has a thickness range of 25 ft on the east side of the L. Wiederkehr lease to 4 ft on the west side. It has a slight overall dip to the North and East of some 33 ft to the mile.

Jan 1, 1953

By John C. Calhoun, Alfred Chatenever

An exploratory study wap made to examine the possibilities of a visual approach in investigations into microscopic mechanisms of fluid behavior in porous media. Appropriate apparatus and techniques were developed so that microscopic phenomena could be recorded on color movie film as well as be observed visually. The observation flow cells in which tlie fluid behavior studies were made were essentially single-layered matrices of spheres between plates. sometimes all-glass, sometimes all-Lucite and sometimes a combination of the two. The fluids were limited to water and a filtered crude oil. Two flow regimes were observed during the flow of the immiscible liquids: channel flow and slug flow. In the former, transport was effected through stable networks of interconnecting channels; and in the latter, part of the movement took place in the form of slugs. Under certain conditions, flood-front patterns were found to be different depending upon which liquids were the displacing and displaced phases and not depending upon whether the matrix was water-wet glass or oil-wet Lucite. Residual formations of oil and water were observed and are described. Some of the ramifications and significance of the ohservetl phenomena are discussed. INTRODUCTION In recent years considerations of microscopic mechanisms of fluid flow in porous media have taken on greater significance. Much needs to be learned before the fundamentals of petroleum technology are completely established. For example, many unanswered questions exist in connection with relative permeability, displacement phenomena, residua! fluid formations. flow structure, etc.; and further analytical mathematical formulations are seriously indicated. It is hoped that systematic investigations into the microscopic mechanisms connected with the behavior of fluids in porous media will shed some light on some of the problems extant. Until recently microscopic mechanisms have been considered almost exclusively as speculative hypotheses. Within the past few years, however, the problem has been submitted to a limited number of experimental investigations. Nuss and Whiting' made some studies on the pore-space geometry of sandstones and limestones by impregnating cores with an inert plastic and leaching the solid matrices to leave behind plastic models of the pore spaces. SchaeferZ traced pore spaces microscopically through lengths of limestone cores by cutting away thin sections from the exposed faces normal to the line of view. In 1949 two projects were organized in which dynamic flow phenomena were examined microscopically to uncover microscopic mechanisms. One was set up at the Pennsylvania State College where Lowmanb bserved heterogeneous fluid flow phenomena in capillaries. The second was the American Petroleum Institute Research Project 47B at the University of Oklahoma where microscopic studies of dynamic fluid phenomena in synthetic porous matrices have been made by visual observation and cinephotomicrography.' It is with the latter that this paper is concerned. treating the techniques involved and the observations made. TECHNIQUES Observation Flow Cells The observation flow cells formed a focal point in the techniques employed. Essentially, these were matrices composed of a single layer of spheres sandwiched between two flat plates. This design was arrived at after a series of pre-

Jan 1, 1952

By Rodolfo V. de la Cruz

The in situ deformability of rock masses is determined by relating the applied load to the radial displacements of points on the borehole wall that are outside of the loaded surfaces. The external displacement method includes the steps in which: a) radial displacement sensors are installed to measure the change in length of a diameter of a borehole; b) unidirectional self- equilibrating pair of forces perpendicular to the direction of radial displacement measurements are applied on opposite sectors of the borehole wall, and; c) using elastic theory, the in-situ deformability of the rock mass can be related with the applied loads and measured radial displacements. The displacements outside the loaded surfaces are comparatively smaller in magnitude than displacements inside the loaded surfaces. These displacements, however, are sufficiently large and can be measured precisely by commercially available linear displacement sensors. Loads are applied by a conventional borehole jack. Existing methods for measuring the in situ deformability of rock masses yields unreliable results due to complex boundary stresses, small and varying contact areas, and the existence of fractures. It was shown that in the external displacement method, the effect of boundary pressure distribution and contact area are negligible. Also, since the displacements measured in the external displacement method were due to materials that are deeper inside the rock mass, borehole fractures have less influence on the calculated deformation modulus.

Jan 1, 1982

By A. Poll, J. E. Stantan, L. J. Jolley

THE basic problem in the generation of water gas from carbonaceous fuels and steam is the supply of the heat of reaction, and in general the source of this heat is the combustion of a further quantity of carbon with oxygen. Existing and proposed processes for complete gasification differ in the methods employed for transferring this heat to the fuel, and involve one or other of the following alternatives: 1. Use of a steam-oxygen mixture as the gasifying medium, so that the combustion and gasification reactions are combined. 2. Alternate passage of air and steam through a fixed bed, as in conventional water-gas production. 3. Cyclic passage of fluidized fuel through combustion and gasification zones. 4. Intense preheating of steam and of a portion of the gas made, and recirculation of this mixture through the fuel bed. 5. Supply of heat to the fuel bed through an externally heated wall. Except for the conventional water-gas process using large coke or low- volatile coal, only processes in the first group, operating with steam and oxygen, have proved practicable with fuels other than brown coals and lignites. A possible exception, which has not so far reached a commercial scale, is the moving-burden process developed by Imperial Chemical Indus- tries, Ltd. The cost of industrial oxygen is so high that its use can probably be justified only if it is attended by substantial savings in other directions; for instance, the use of cheap fuel. In the United Kingdom, no very cheap solid fuels are available, and it is unlikely that an oxygen-gasification process could compete economically with conventional production of blue water gas from coke. Hence particular interest attaches to all possibilities of making water gas without using oxygen, if any possible saving in fuel or other costs is involved. The cheapest and most abundant coals in the United Kingdom are the low-rank noncaking bituminous coals in small and ungraded sizes, typically those from the East Midlands coal field, and-fines of high ash content produced in coal-cleaning operations. A process capable of gasifying

Jan 1, 1953

C. W. WASHBURNE; New York; N. Y. (communication to the Secretary *).-It has long been known that sulphur and oxygen react upon crude oils, removing hydrogen and thereby creating unsaturated hydrocarbons which unite with each other, producing heavier forms. Dr. Rogers now finds that the percentage of sulphur in the oils of several fields in California is roughly proportional to the specific gravity of the oil. This additional proof is most welcome. It is rather surprising, , in that the impression had prevailed that practically all the reacting sulphur escaped from the oil as hydrogen sulphide, and did not remain in combination with the oil. It would be interesting to know what part of the sulphur-plotted by Dr. Rogers is in solution as free sulphur and hydrogen sulphide, and what part is, in more complex compounds, such as thiophanes, etc.

Jan 10, 1917

By Peter L. Swanson

A microcrack process zone is frequently suggested to accompany macrofractures in rock and play an important role in the resistance to fracture propagation. Attenuation of surface waves propagating through mode I fractures in wedge-loaded double-cantilever beam specimens of Westerly granite has been recorded in an attempt to characterize the structure of the fracture process zone. The ultrasonic measurements do not support the generally accepted model of a macroscopic fracture that incrementally propagates with the accompaniment of a cloud of microcracks. Instead, fractures in Westerly granite appear to form as gradually separating surfaces within a zone having a width of a few millimeters and a length of several tens of millimeters. A fracture process zone of this size would necessitate the use of meter-sized specimens in order for linear elastic fracture mechanics to be applicable.

Jan 1, 1984

By W. P. Haynes

No wildcat operations are recorded from France during the past year, and no new discoveries have been made. In northern Africa, in Morocco, some prospecting continued in the Gharb and Tselfat regions. Only very small production or shows were found. At the close of the year one cable-tool well (depth 400 meters) was drilling in the Tselfat district, and one rotary well in the Gharb. In Tunisia one well was drilling at Sloughia. Refinery building has been active under the new petroleum law, no less than six plants now being under construction. At Pechelbronn, it is estimated 130 wells were drilled, of which 73 wells, or 56 per cent, were productive. Total drilling was 45,000 m. One new Jurassic horizon was discovered. In the mining area approximately 17,500 m. of new gallery were driven. Production at Pechelbronn for the first nine months was as follows: From wells, 233,013 bbl.; from mines, 164,815 bb1.—a total estimated production for the year of 532,000 bbl. Production at Gabian was 3780 bbl. for the year. In Algeria production from Tliouanet was small, being estimated at 6510 bbl. This production is from Helvetian sands (Miocene) around a salt plug. Italy Production for the year was 211,500 bbl., an increase of 62 per cent over that of last year. Drilling to the extent of 97,000 ft. was done mainly by the A. G. I. P., the government company in the Province of Emilia. More locations are being tested in this area, where geophysical results have shown indications of buried uplifts. Oil has been encountered on two of these structures, at Fontevivo and Podenzano, but the wells have given trouble with salt water. The chief producer is the Societa Petrolifera Italiana at Salsomaggiore and Valezza. The production is from sand lenses at relatively shallow depths. New concessions of 2000 hectares were granted at several points in the Po Valley, and geophysical work is being carried on. The A. G. I. P. is working on a five-year program of exploration to test new areas.

Jan 1, 1933

By Leonard Greenburg

The American literature in the field of dust sampling and analysis has been growing rapidly since 1915. Studies made since that time clearly indicate that there are three fundamental factors that determine the production of lung pathology due to dust inhalation. These are the duration of exposure, the chemical and mineralogic nature of the dust and the concentration of the potentially harmful dust. In the estimation of the amount of the potentially hazardous dust there are essentially three problems involved: (I) a determination of the size of the hazardous dust; (2) determination of the most satisfactory apparatus and technique of sampling, and (3) the most satisfactory method of analysis. A complete study of the literature shows that industrial dust varies ill size from ultramicroscopic particles to those larger than lop in diameter and that relatively few particles are found over 5u in diameter. Approximately 10 to 25 per cent are less than 0.811 in diameter and the median size as a rule is found to lie between 1.25 and 1.75 microns. From the point of view of lung pathology the particle sizes of most importance lie between 0.5 and 5u. Of all the instruments for sampling dust the Impinger apparatus is the only one that will sample a larger body of air satisfactorily with small control errors and high efficiency in both low and high concentrations of dust. The Owens apparatus has the advantage of being more portable and somewhat easier to use but it does riot permit of the sampling of large volumes of air. It has a low efficiency in high concentrations of dust and does not permit dust weights to be obtained. From the point of dust-counting technique the author points out that in 1922 considerable experimentation with dark field and oblique illumination resulted in the conclusion that such methods were not readily duplicated from day to day and therefore yielded somewhat erratic results. Changes in the amount of illumination produced variations of several hundred per cent in dust counts obtained with dark ground

Jan 1, 1934

By James F. Kemp

In earlier gears, the custom prevailed of regarding the anthracite basins as cases of folding with slight development of faulting. Folding is so pronounced and, in the eastern and western Middle Fields, at times so violent, that the inference was a natural one and led to the widespread impression that practically all the disturbances of the seams could be explained in this way. The cross-sections and maps prepared forty or more years ago for the Second Geological Survey of P ennsylvania, by Mr. Ashburner under Prof. J. P. Lesley, exhibit little else than folds.' So far as I can discover faults fail in the charts, except in one small case in the Henry colliery near Plainsville on the outskirts of Wilkes-Barre. Some years ago, while spending a day or two in Wilkes-Barr, under the guidance of R. V. Norris, I looked over some recent and accurate cross-sections of a numbcr of the large collieries and was deeply impressed with the peculiar behavior of some of the seams and the intervening shales. Thus, a seam might present a small, more or less overturned fold, rising 30 to 50 ft. (9 to 15m.) above its general course, and yet the movement would be taken up in the overlying shales, so as hardly to be noticeable in the seams next above or below. These and similar anomalies, especially when shown with the accuracy of engineer's surveys, possess great scientific and practical interest, bearing as they do, not alone on coal mining, but on theoretical geology and the actual behavior of strata under great compressive stresses. In preparation for the semicentennial meeting of the Institute, an effort was therefore made to secure some of the most interesting sections for presentation to the members. The collection of illustrations here shown is mainly due to Douglas Bunting of the local committee, to whom and to the contributing companies acknowledgments are due. The illustrations are taken from all four of the main basins, but are chiefly from the portions nearest Wilkes-Barre. The first are in the

Jan 1, 1922

By Robert W. Hunt

The memorable features of American history have been making fast during the last century, and notably so since 1860; and they are by no means confined to political or to any one branch of scientific development. Of all the industrial arts, none show a greater change or 'a mightier progress than the Bessemer manufacture. And this year, while we are celebrating the first centennial of our national life, we can also celebrate the first decennial of American Bessemer practice. While not forgetting or undervaluing what has been done in other countries, I have thought that a brief history of the introduction and development of the Pneumatic or Bessemer process in America would be of interest. In 1863 the Kelly Pneumatic Process Company was formed and an arrangement entered into with William Kelly, who had taken out letters-patent of the United States, Nos. 16,444; 17,628, reissued as 505; 18,910, dated January loth, 1857; June 23d, 1857; November 36, 1857; and December 22d, 1867, respectively. This association mas composed of the Cambria Iron Company, E. B. Ward, Park Brothers & Co., Lyon, Shorb & Co., Z. S. Durfee, and, later, Chouteau, Harrison & Valle joined the combination. Not satisfied with possessing the control of the Kelly patent, they sent Mr. 2. S. Durfee to England, to secure for this country Mushet's patent on recarburization, No. 17,389, dated May 26th, 1857, the same having been taken out in England on September 22d, 1856. In this Mr. Durfee was successful. Previous to the application of William Kelly for a patent, Henry Bessemer, of England, had taken out patents dated February 12th, 1856, and August 25th, 1856, in this country. Kelly claimed priority in the discovery of the principles of the process, and the Patent-office allowed his claim by granting him his patents. In the autumn of 1862 Mr. Alexander L. Holley, while in England, was impressed with the importance of Mr. Bessemer's invention, and so fully foresaw its future, that, upon his return to the United States, he induced Messrs. John A. Griswold and John F. Winslow, of Troy, New York, to join him in endeavoring to possess Bessemer's American patents. Mr. Holley returned to England in

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent investigations1. a data on relative grain boundary energies in silicon iron have been obtained. The present investigation is a continuation of this work along similar lines for the purpose of obtaining additional information on boundary energies. One aim has been to extend the data for a (110) series, which was formerly studied,' to small differences in orientation, since a recent theory3,4 based on a dislocation model of grain boundaries predicts a E. ? (A-ln ? )* form of energy curve for small differences in orientation. Another aim has been to provide data for a (100) series—all grains having (100) planes parallel with the surface of sheet speci-mens—and to compare the results with the predicted form of energy curve. Finally, information on the nature of approach to equilibrium conditions was to be obtained through observations on the movements of grain boundaries. Recently published papers2,3,5 have treated the mathematical problem of expressing equilibrium conditions for grain boundaries for the general case when boundary energy depends upon boundary orientation. The equilibrium equations, which relate equilibrium angles and grain boundary -free energies, contain additional terms that express the variation of energy with boundary rotation. It has been necessary in the present investigation, however, to neglect these additional terms since no data for their evaluation were available. Dropping the additional terms leads to the following approximate equations which were used: E12/sin ?3 = E18/sin?2 =E28/sin?1 or those of the form: E28 + E13 cos ?3 + E12 cos ?2 = 0 Experimental Procedure Except for sample F1, all specimens were made from two lots of silicon iron called C and L respectively. The compositions of these are listed in table I. In the preparation of 12 three-grain specimens for the present investigation, a controlled grain growth technique, which has been described previously,' was used. After preparation, the specimens were notched at the boundaries to shorten them as a means of providing more rapid approach to equilibrium in the anneals. Initial grain boundary angles were determined from micrographs taken at X500. Seven anneals, totaling about two days at 1300°C and two to four days at 1400°C, were run in an atmosphere of pure dry argon as described in a previous paper.' Boundary changes generally could be followed without metallographic surface preparation, because thermal etching occurred during the anneals. These observations indicated angle changes of as much as 35" in some instances, with the major changes occurring during the first anneal. Annealing was discontinued when the angles reached stationary values. Fig. 1 gives a schematic diagram for purposes of defining crystallographic and boundary directions for three grains with common plane parallel with the sheet. Differences in orientations (expressed by A) are the angles between [00l] directions. They can be calculated with the aid of the ?'s. The grain boundary angles can be calculated from the w'S. Results Results are given in table 11. Types of crystal-lographic planes refer to those parallel with the sheet. Orientations are given in terms of [00l] direc-tions as shown in fig. 1. Except for grain 3 of specimen H6, which was unintentionally tilted 7" out of a (100) plane, all grains generally were within 1" or 2" of the plane specified. The directions of boundaries were measured generally to within 1" on both upper and lower surfaces, and the average direc- tions were determined for use in calculating the grain boundary angles. Variations in grain boundary directions refer to deviations from average directions. Boundaries near the junction point for all specimens generally were very close to perpendicu-

Jan 1, 1951

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst' and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick's3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,' and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"' have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol' and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.'' Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1'

Jan 1, 1961

By Paul A. Beck

THE occurrence of the (100) [lOO] or "cube" texture upon annealing of cold-rolled copper has been much investigated.' The conditions favorable for its formation were found to be a high final annealing temperaturez or long annealing time," a high reduction of area in cold rolling prior to the final anneal,' and a small penultimate grain size." The effects of penultimate grain size and of rolling reduction were found by Cook and Richards4 to be interrelated in such a way that any combination of them giving lower than a certain value of the final average thickness of the grains in the rolled material leads to a fairly complete cube texture with a given final annealing time and temperature. Also, according to the same authors, at a higher final annealing temperature a larger average rolled grain thickness, i.e., a lower final rolling reduction, is sufficient than at a lower temperature. These somewhat involved conditions can be understood readily on the basis of recent results obtained at this laboratory. Hsun Hu was able to show recently by means of quantitative pole figure determinations that the rolling texture of tough pitch copper, which is almost identical with that of 2s aluminum: may be described roughly as a scatter around four symmetrical "ideal" orientations not very far from (123) [112]. In the case of aluminum, annealing leads to retain-ment of the rolling texture with some decrease of the scatter around the four "ideal" orientations, and to the appearance of a new texture component, namely the cube texture." A microscopic technique, revealing grain orientations by means of oxide film and polarized light, showed that the retainment of the rolling texture is achieved through two different mechanisms operating simultaneously, namely "re-crystallization in situ," and the formation of strain-free grains in orientations different from their local surroundings, but identical with that of another component of the rolling texture. Thus, a local area in the rolled material, having approximately the orientation of one of the four "ideal" components of the texture, partly retains its orientation during annealing, while recovering from its cold-worked condition, and it is partially absorbed at the same time by invading strain-free grains of an orientation approximately corresponding to that of another "ideal" texture component. The reorientation here, as well as in the formation of the strain-free grains of "cube" orientation, may be described as a [Ill] rotation of about 40°, see Fig. 1 of ref. 6. The preferential growth of grains in such orientations is a result of the high mobility of grain boundaries corresponding to this relative orientation.' " It appears very likely that in copper the mechanism of the structural changes during annealing is similar to that observed in aluminum (except for the much greater frequency of formation of annealing twins in copper). In both metals the new grains of cube orientation have a great advantage over the new grains with orientations close to one of the four components of the rolling texture. This advantage stems from their symmetrical orientation with respect to all four retained rolling texture components of the matrix; they are oriented favorably for growth at the expense of all of these four orientations. As a result, the growth of the "cube grains" is favored over the growth of the others, as soon as the new grains have grown large enough to be in contact with portions of the matrix containing elements of more than one, and preferably of all four component textures. It is clear that this critical size is smaller and, therefore, attained earlier in the annealing process if the structural units, such as grains and kink bands, representing the four matrix orientations are smaller, i. e., if the average thickness of the rolled grains is smaller. Hence, for a given annealing time and temperature, a smaller penultimate grain size and a higher rolling reduction both tend to increase that fraction of the annealing period during which the above condition is satisfied. Consequently, the percentage volume of material assuming the cube orientation increases. The same is true also for increasing time and temperature of annealing when the penultimate grain size and the final rolling reduction are constant, since the average size attained by the new grains during annealing increases with the annealing time and temperature. For the same reason, at higher annealing temperatures a given volume percentage of cube texture can be obtained with larger rolled grain thickness (larger penultimate grain size, or smaller rolling reduction) than at lower annealing temperatures. The well-known conspicuous sharpness of the cube texture may be interpreted as a result of the fact that selective growth of only those grains is favored that have an orientation closely symmetrical with respect to all four components of the deformation texture and exhibit, therefore, a high boundary mobility in contact with each. The effect of alloying elements in suppressing the cube texture, as described by Dahl and Pawlek,' appears to be associated with a change in the rolling texture. For face-centered cubic metals, such as copper, which do exhibit the cube texture upon annealing, the rolling texture is always of the type described above, i. e., scattered around four "ideal orientations" of approximately (123) [112]. The addition of certain alloying elements, such as about 5 pct Zn or 0.05 pct P in copper, has the as yet unexplained effect of changing the rolling texture into the (110) 11121 type. This texture consists of two fairly sharply developed, twin related components. In such cases, as in 70-30 brass and in silver, the annealing texture again is related to the rolling texture by a [lll] rotation of about 30°, however, because of the different rolling texture to start from, it has no cube texture component. At higher temperatures, both in brassm and in silver," grain growth leads to a further change in texture: A [lll] rotation of the same amount, but in reversed direction, back to the original rolling texture.

Jan 1, 1952