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By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

A dinner was given to Ambrose Swasey by the United Engineering Society, at the Engineers' Club, on November 14. Those present -included -twenty-one presidents and past presidents of the Founder Societies. Charles F. Rand, President of United Engineering Society, presided. President Robert S. Woodward, of the Carnegie Institution of Washington, and Dr. Robert W. Hunt, of Chicago, made addresses to which Mr. Swasey responded. Dr. Michael I. Pupin, Chairman of Engineering Foundation, made the closing address. The evening was marked by the high character of the addresses, inspiration for grave duties lying before the engineering profession, and by the spirit of good fellowship. Among the seventy-two persons present were the following members of the Institute: E. E. Bartlett, William N. Best, J. Parke, Channing, C. R. Corning, F. C. Cottrell, J. V. Davies, J. V. N. Dorr, H. S. Drinker, Karl Eilers, H. M. Howe, A. C. Humphreys, Robert W. Hunt, Wm.. B. Jackson, D. S. Jacobus, J. H. Janeway, J. E. Johnson, Jr., John Johnston, George F. Kunz, Edwin Ludlow, Philip N. Moore, Fred'k. H. Newell; Wm. H. Nichols, H. Hobart Porter, Charles F. Rand, R. M. Raymond, .Jesse M. Smith, E. Gybbon Spilsbury, Bradley Stoughton, . Joseph Struthers, Benj. B. Thayer, Wm. H. Wiley, S. T. Wellman.

Jan 1, 1919

PROF RICHARD ÅKERMAN Stockholm, Sweden PROF RICHARD BECK Friberg, Germany ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England PROF HANS HOFFER Leoben, Austria PROF HENRI LOUIS LE CHATELIER Paris France M FLORIS OSMOND Paris, France ALEXANDRE POURCEL Paris, France JOHN E. STEAD Middlesborugh, England DR. ING H. C. EMIL SCHROEDTER Dusseldorf, Germany JAMES M. SWANK (Associate) Philadelphia, Pa. PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF TSUNASHIRO WADA Tokyo, Japan CHARLES D WALCOT Washingtion D.C.

Jan 1, 1917

By R. W. Raymond

THIS meeting was held in the new home of the Institute, the United Engineering Society Building, 29 West 39th Street, New York City, directly following the Dedication ceremonies. The first session was held in the large Auditorium, Thursday, April 18. The meeting was called to order by Mr. John Hays Hammond, President of the Council, who said Before taking up the reading and discussion of papers, I will call upon Dr. Rossiter W. Raymond, the oldest living past-President of the Institute, who has been in harness almost continuously for thirty-six years, and who has contributed more than any one else to bring this society to its present great success and to establish the reputation of the American mining engineer the world over, for a few words supplementary to those which were uttered to engineers generally, during the sessions of yesterday and the day before. ADDRESS BY R. W. RAYMOND. The generally accepted Darwinian doctrine of the survival of the fittest is sometimes illustrated by persons who are supposed to be the fittest because they have simply survived. I fear that I come under that category. Almost all of my contemporaries in the early history of this Institute have passed away. Only one or two of the original founders remain, and I may fairly say that scarcely any remain who were active at that : time in shaping the organization and the future career of the Institute. In May, 1871, I was thirty-one years old. Next week I shall be sixty-seven years old. All the intervening years have been devoted to the service of this Institute almost continuously, either as President or Vice-President or Secretary. You may easily imagine, therefore, with what pleasure I greet you on this occasion. I am not here to extend to you the welcome of the City - of

May 1, 1907

By Harold Vance

The Lafitte field, the largest oil reserve in South Louisiana, is in Jefferson Parish, some 25 miles due south of the City of New Orleans. The discovery well, The Texas Company's No. I, Louisiana Land and Exploration Co., in the southeast corner of sec. 19, T. 17 S., R. 24 E., was completed on May 15, 1935. The initial production of this well was 960 bbl. of 34.9º A.P.I, gravity oil per day, through 1/4-in. choke, with a tubing pressure of 1600 lb. per sq. in. Producing depth was 9558 to 9572 ft., the total depth being 9572 feet. The development of the field has been at the rate of three to eight new producing wells per year. Up to Jan. I, 1944, 60 producing wells and three dry holes had been drilled, while two of the original producing wells had been abandoned, Although the field is not unitized, The Texas Company was the sole operator in the field until the Lafitte Oil Co. completed its NO. I Jefferson Parish, near the center of the west line of the NW/4 sec. 20, T. I7 S., R. 24 E., on July 27, 1941. No additional wells have been drilled by the Lafitte Oil Company. Drilling and WeLl-completion Practices All drilling operations have been conducted with the steam-driven rotary equipment mounted on submersible barges. A canal is dug to the well location and the drilling unit is floated into position. The seacocks are then opened and the barge settles to the bottom. After the well is completed, seacocks are closed and water is pumped out of the barge. This procedure permits the barge, with drilling equipment still in place, to be floated and moved off the location. The conventional open-hole and the gun-perforation method of completing wells has been used in this field. Where possible, the initial completion is from the deepest 'sand and recompletions are made progressively up the hole, by plugging back with cement to the upper sand and gun-perforating opposite the new sand. The oil string usually is 7 5/8 in., 26 to 34-lb. casing. Three wells have been completed using 9 5/8-in. 44-lb casing set below 10.000 feet. Fig. I shows the completion and recom-pletion practices on one well in the field. This figure also shows the relative locations of the different producing sands as shown on the electric well log. Structure The structure is an elongated dome, cut by two north-south faults, which divides the field into three segments. The west segment is the highest structurally and contains most of the recoverable oil and gas. The center segment is less important and the east segment is of little value. Figs. 2, 4, 6, 8 and 10 are depth contour maps on top of the five main producing sands in the field. These maps show the relative size of the five reservoirs and the

Jan 1, 1945

Organization Place Date 1919 National Drainage Congress St. Louis, Mo. Nov. 11-13 American Mining Congress St. Louis, Mo. Nov. 1.7-21 Canadian Mining Institute Vancouver, B. C. Nov.. 26-28 American Society of Mechanical Engineers:.... New York, N. Y. Dec. 2-5 American Institute of Chemical Engineers Savannah, Ga. Dec. 3-6 Geological Society of America...; Boston, Mass. Dec. 29-31. American Society of Heating and Ventilating 1920 Engineers New York, N. Y. Jan. Mining and Metallurgical Society of America ... New York, N. Y. Jan. 13. American Institute of Min. and Met. Engineers... New York, N. Y. Feb. 16-19 American Ceramic Society Philadelphia, Pa. Feb. 23-26

Jan 11, 1919

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

?AARONSON, ALFRED E, .Vice-Pres, Mid-Co Petroleum Co , Mid-Co Bldg, Tulsa, Okla '18 ABADIE, EMILE R, Min Engr - Box 927, Porterville, Cal '76 ||ABADILLA, QuiRiCo A, Student, Colorado School of Mines, Golden, Colo. '20 ABBOTT, CLARENCE E, Gen'l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co , 1405 Minnesota Ave, Bessemer, Ala. '04 ABBOTT, Louis BENJAMIN, Chief Engr, Consolidation Coal Co-, Elkhorn Div, Jenkins, Ky '15 ABBOTT, ROBERT R Met. Engr, Peerless Motor Car Co, Cleveland, Ohio. '12 ABE, ASAKA Fujita Min Co, Dojima, Osaka, Japan '14 ABEEL, GEORGE H, JR, Cons Min Engr, 633 St Paul Ave, Los Angeles, Cal '18 ABEL, ALBERT E, Mgr., Pittsburgh Dist, Valley Mould & Iron Corpn, 28th St & R R Ave, Pittsburgh, Pa '19 ABEL, W D, Min. Engr. 3897 Sacramento St , San Francisco, Cal. '19 ABELL, 0 J, Pres & Treas, Abell-Howe Co, 332 South Michigan Ave, Chicago, Ill '19 ABERNATHY, G E Willow Springs, Mo '20 ABEY, HIROSHI, Min & Met Engr, Arakawa Mine, Mitsubishi Co, Senpoku-gun, Akitaken, Japan '17

Jan 1, 1923

[Separates of all the Technical Publications published in 1929 are available at lnstitute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the Transactions.] Metal Mining Technical Pdbli- Title Author Meeting Trans. cation . Volume No. and Page* 182-A-23 The Royal Commission on Mining Henry Louis New York Subsidence Feb., 1929 183-A-24 Cycles in Metal Production D. F. Hewett Nen. York T29, 65, 95 Feb., 1929 199-A-25 Ventilation at the United Verde Oscar A. Glaeser New York T29,- 114. Mine Feb., 1929 206-A-26 Air Conditioning In Deep Mines R. W. Waterfill New York T29. 99, 112 Feb., 1929 245-A-27 Bumps in No. 2 Mine, Springhill, Walter Herd New York Nova Scotia (with discussion) Feb., 1929 257-A-28 Misfires: Their Causes, Prevention New York and Treatment on Occurrence Feb., 1929 Misfires in Anthracite Coa1 T. D. Thomas Mines (With Discussion) Misfires in Bituminous Coal W. H. Forbes Mines (With Discussion) Misfires in Non-metallic Mining A. W. Worthington (Limestone) (With Discussion) Milling and Concentration 195-B-15 A Study of Differential Flotation C. R. Ince New York Feb., 1929 196-B-16 Elements of Operation of the Arthur F. Taggart New York Pneumatic Table H. L. Lechmereoertel Feb., 1929 202-B-18 Silver-bearing Minerals of Some A; W. Habn New York T29, 325 Ores from Tintic Mining District Feb., 1929 204-B-17 Experiments with Flotation Re- A. F. Taggart New York agents T. C. Taylor Feb., 1929 C. R. Ince 208-B-20 Cyanide Regeneration or Recov- C. W. Lawr Sun Francisco ety as Practiced by the Com- Oct., 1929 pania Beneficiadora de Pachuca, Mexico 214-B-19 Calculations in Ore Dressing W. Luyken New York E. Bierbraer Feb., 1929 217-B-21 Differential Grinding Applied to Leon M. Banks San Francisco Tailing Retreatment George A. Johnson Oct., 1929 224-B-22 Reducing and Oxidizing Agents Research Staff San Francisco and Lime Consumption in Flo- of United Verde Oct., 1929 tation Pulp Copper Co. 247-B-23 Copper Sulfate as Flotation Acti- 0. C. Ralaton San Francisco vator for Sphalerite 0. R. King Oct., 1929 F. X. Tartaron

Jan 1, 1929

By T. S. Lundy, C. J. McHargue

HE diffusion rate of v48 in single crystals of bee vanadium has been determined at temperatures from 1002° to 1888°C. Standard techniques of lathe sectioning were used for specimens annealed above 1500°C while sectioning by grinding was used for specimens annealed at lower temperatures. As will be seen, the lower-temperature data is enhanced on an Arrhenius-type plot relative to values expected by extrapolation of the high-temperature data. Single crystals were obtained from Linde Co. In Table I the analysis supplied by the vendor is compared with an analysis at Oak Ridge National Laboratory of a sample after a diffusion anneal. The isotope v4' was prepared by the Isotopes Division of Oak Ridge National Laboratory. Proton bombardment of a titanium target in the 86-Inch ORNL Cyclotron was followed by a carrier-free chemical separation. Nineteen specimens, 1/2 in. diam and 3/8 in. long, were cut from the as-received vanadium single crystals. Each specimen was machined with the flat face perpendicular to the longitudinal axis. Specimens were polished through 1/0 emery paper and were etched with 25 pct HF-10 pct H2SO4-10 pct HNO3-55 pct H2O. The polishing and etching steps were repeated until a satisfactory surface finish was achieved. The isotope was electroplated onto the specimens from a neutral solution. Counting rates of the deposited layers were approximately 100 counts per sec. At temperatures above 1200°C specimens were annealed in a tantalum resistance furnace under an argon atmosphere. Temperatures were measured with a Pyro micro-optical pyrometer and a Pt-Pt 10 pct Rh thermocouple. At lower temperatures the specimens were sealed in evacuated quartz ampoules and annealed in Kanthal wire-wound horizontal tube furnaces. A severe reaction occurred at 1200°C between the quartz and the vanadium. This

Jan 1, 1965

By Walter Lang

The year 1931 has shown a marked change over 1930 in New Mexico, with respect to the volume of activities attendant upon the petroleum industry. Although the total production of oil and gas this year exceeds that of preceding years, the results have been attained from established units operating under restriction, but capable of supplying far more than the economic conditions justify. The presidential order of March 12, 1929, that "there will be complete conservation of Government oil in this administration," has merely anticipated a normal consequence of overdevelopment. As a result of the combined economic and legal restrictions imposed, very little new drilling has occurred during the year. Even in proven areas the drilling of offsets has been curtailed to the absolute limit of requirements. Scouting and sample-cutting, which in 1930 were still in a state of feverish activity, are at low ebb, and lease buying has reached a condition of stagnation. A number of the major oil companies have either materially reduced their field and office forces or completely eliminated local office representation. Two tests of particular interest, because correlation shows them to be structurally high although they failed to produce, are the National Securities well drilled six miles west of the town of Hobbs, on sec. 33, T.18 S., R.37 E., Lea County, to a total depth of 4272 ft., which developed a flow of 4,000,000 cu. ft. of gas at 3860 ft., and a show of oil; and the Western Drilling Co. No. 1 State, sec. 16, T.20S., R.32 E., Lea County. The latter test found dead oil at 2575 to 2580 ft., and sulfur water at 2745 ft., increasing to 2780 ft., representing the zone from which production was generally expected. The well was drilled to 4013 feet. The discovery of sulfur at about 950 ft. in the deepening of an old water well (Pearson, NE. 1/4 sec. 8, T.16 S., R.25 E.) drilled in the Little Cottonwood area northwest of Artesia led the Union Sulphur Co. to drill three prospect tests on a block of acreage in the vicinity during the summer and fall. The results of the investigation have not been disclosed. The Kummbaca Oil and Gas Co. drilled the T. J. Kerline No. 1, in sec. 34, T.21 N., R.30 E., Harding County, gaging 3,654,000 cu. ft. of 98 per cent CO² at 940 ft. The Barton structure, 20 miles east of Albu-

Jan 1, 1932

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

Organization Place Date 1918 American Chemical Society Cleveland, 0. Sept. American Society of Sanitary Engineers Chicago, 111. Sept. National Petroleum Association Atlantic City, N. J. Sept. American Institute of. Mining Engineers Colorado Sept. 2-7 National Association of Stationary Engineers.... Cincinnati, 0. Sept. 9-13 Association Iron, Steel, Electrical, Engineers Baltimore, Md. Sept. 9-14 British Iron and Steel Institute, Autumn Meeting London, Eng. Sept. 12-13 National Exposition of Chemical Industries New York, N. Y. Sept. 23-28 American Electrochemical Society Princeton, N. J. Sept. 30¬Oct. 2

Jan 8, 1918

By Clarence Zener

The internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites, localized weak regions introduced by cold-working,6'7 grain boundaries and possibly twinning planes.8'9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3.i in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff. Experimental Method The experimental method used has previously been described in institute papers.5'6'9 The measure of internal friction adopted here, I/Q, is X the logarithmic decre- ment, a measure used by some writers, and is also X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. Experimental Results The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. I, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of 100 during the next Ioo° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e-H/RT [I]

Jan 1, 1943

By Clarence Zener

The internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites, localized weak regions introduced by cold-working,6'7 grain boundaries and possibly twinning planes.8'9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3.i in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff. Experimental Method The experimental method used has previously been described in institute papers.5'6'9 The measure of internal friction adopted here, I/Q, is X the logarithmic decre- ment, a measure used by some writers, and is also X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. Experimental Results The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. I, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of 100 during the next Ioo° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e-H/RT [I]

Jan 1, 1943

By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3'4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

Jan 1, 1887

By W. E. C. Coxe

IN 1857 the Philadelphia and Reading Railroad Company, whose main line extended from Philadelphia to Pottsville, Pennsylvania, with branches into the coal regions of Schuylkill County, made a contract with the Fairmount Rolling Mill, at Philadelphia, for the rerolling of some four thousand tons of iron rails. The essential features of the agreement were that the old rails should be piled with puddled iron and rolled into flats for the rail pile, which latter was to be of a section seven inches square, and after being heated, and reduced, by rolling, to a bloom of a section about five inches by six inches, was to be reheated, before being finished into the rail of the T pattern, four inches high, weighing sixty-four pounds per yard. Great care was exercised in the execution of this contract, and the rails being distributed over all parts of the road, gave general satis¬faction by their excellent wear. Five years afterward, the principal proprietor and manager of the Fairmount Rolling Mill was elected President of the Reading Railroad, and very many of the rails made under his supervision were still in use in the tracks of the company, of which he had just assumed the management. His first efforts were, therefore, directed to the procuring of more rails of the same quality wherewith to replace those worn out. Here he encountered some trouble, makers refusing to bid because of the details in the specification, the required reheating being the objectionable feature, for which it was generally intimated they would not be sufficiently remunerated for the increased labor, extra coal consumed, and the changes necessary from the established methods of working. Most of the new rails were, therefore, bought, and the old rails rerolled without regard to any particulars as to the manner of piling, heating, etc., each manufacturer furnishing what he deemed the best article possible for the money. As a consequence, rails of all imaginable grades were placed in the tracks, some giving out in six

Jan 1, 1877

By Frederick G. Bulkley

That portion of the geological structure of the Leadville district which rests upon the Archæan is made up of sedimentary beds of Silurian and Carboniferous formation, consisting of many conformable strata of limestones, quartzites, and shales, which have a total present thickness of about five thousand feet. Interbedded with these strata are found, under somewhat fixed lams of regularity, sheets of intrusive igneous rock,' varying in thickness from a foot or two to several hundred feet. These consist for the most part of various types of felsite rocks, classed, by the sanction of common and long-continued usage, under the general term of porphyries. Mr. S. F. Emmons, in the abstract of his " Report upon the Geology and Mining Industry of Leadville," says in this connection : In their mode of occurrence the type-feature is that of intrusive masses, which are developed on a scale of unprecedented magnitude, and follow certain horizons with remarkable regularity.... It is probable that this mode of occurrence of eruptive rocks, viz., as intrusive masses which originally did not reach the surface but were forced up to a certain horizon and then spread out bettween the beds, is far more common than has hitherto been suspected by geologists. It is difficult to conceive of the conditions under which a fused mass could pry open strata to a width of one thousand feet or more, overcoming the weight often thousand feet of superincumbent rocks, and spread itself out in a continuous sheet between the beds to a distance of ten miles beyond the point or line of eruption. That they did exist, however, can be clearly demonstrated in this region.... In one single section over fifteen sheets, many several hundred feet thick, were counted between the Blue Limestone and the top of the Carboniferous. The region here under discussion is made up of a series of great

Jan 1, 1885