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By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

NORTH AMERICA ALASKA Anchorage.-Neitzert, G. H. Strandberg, H. Candle.-Robbins, J. S. College.-Barber, R. J. Burns, W. T. Coats, R. R. Fox. E. F. Joesting, H. R. McAnerney, J. M. Colorado Station.-Beyer, A. Stanford, J. V. Douglas.-Cahill, W. E. Carlson, L. Fairbanks.-Crawford, J. D. Earling, R. B. Fowler, D. A. Greves, J. H. Henton, H. M. Herbert, C. F. Hopkins, J. E. Kreitlow, E. J. MacDonald, D., III Mathews, T. C. McCarty, W. J. McNair, W. H. Metcalfe, J. B. Mikami, H. M. Mize, R. J. CANADA ALBERTA Calgary.-Johnson, R. V. Link, T. A. Marple, L. E. Slipper, S. E. Thorne, B. L. Thorne, H. L. Vissac. G. A. Edmonton.-Ball, -M. W. Lilge, E. O. Pitcher, N. C. Nordegg.-Shanks, J. BRITISH COLUMBIA Allenby.-Lindsay, W. R. Bralorne.-Almstrom, A. A. Bosustow, R. Currie, J. M. Gibson, S. Schmitt, D. E. G. Wilson, G. H. Bridge River.¬Botterill, T. C. Crane, G. A.

Jan 1, 1939

By Walter R. Hibbard, George H. Eichelman, William P. Saunders

INTEREST in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,1 has resulted in the application of similar heat treatments to other eutectoid transformations. Studies2.3.4 of the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5,6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported' as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. PREPARATION OF ALLOYS The copper-silicon alloy equilibrium diagram is shown in Fig I. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutectoid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct). Smith5 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.7 Following the casting techniques of Krynitsky, Saunders and Stern,8 the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under the melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X ¾ in., was annealed at 750°C for 21 brand furnace cooled. About 1/16 in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. methods.9 The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1948

By C.P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By C. P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By AIME AIME

COMMITTEES. CENTRAL GENERAL COMMITTEE.-Wm. Fleet Robertson, Chairman; Win. M. Brewer,. Secretary. LOCAL COMMITTEE OF NELSON, B. C.-A. S. Farwell, Chairman; W. C. Bayly, Secretary; William Blakemore, M. S. Davys, S. S. Fowler, R. R. Hedley, Leslie Hill, A. H. Telly; W. C E. Koch, J. J. Campbell. LOCAL COMMITTEE OF ROSSLAND, B. C.-His Worship Mayor Hamilton, Chairman; AV. H. Aldridge, Charles Biesel, H. H. Claudet, F. W. Guernsey, R. Marsh, J. W. Astley, R. W. Brock, A. A. Cole, A. G. Larsen, R. H. Stewart. Also the Rossland Board of Trade, Robert Hunter, President; K. E. Mackenzie, Vice-President; A. B. Mackenzie, Secretary. LOCAL COMMITTEE OF GRAND FORKS, B. C.-His Worship Mayor Hammor, Chairman ; A. W. B. Hodges, A. L. White, G. M. Fripp, L. A. Manley, W. T. Spier, G. W. Wooster. LOCAL COMMITTEE OF VICTORIA, B. C.-Wm. Fleet Robertson, Chairman; William Al. Brewer, Secretary; Harold Grant, Thomas Kiddie, Clermont Livingston, E. C. Musgrave, W. J. Sutton, Francis A. Thomson. LOCAL COMMITTEE OF VANCOUVER, B. C.-C. F. Jackson, Chairman; His Worship Mayor F. Buscombe, J. J. Banfield, A. Bethune, John Boyd, H. C. Clarke, A. B. Erskine, E. P. Gilman, William Godfrey, W. D. Haywood, R. K. Houlgate, H. T. Lockyer, J. I. McAdam, H. M. McDowell, C. W. McMeekin, W. H. Malkin, F. Richards, T. J. Smith, George A. Walkem, G. Slieldon Williams. LOCAL COMMITTEE OF WHITE HORSE, Y. T.-Robert Lowe, Chairman.; T. W. Jackson, Secretary; George -Armstrong, A. L. Bindley, Rev. Father Corbeil, L. De Gex, A. E. Fisher, W. P. Grainger, P. D. McMillan, Rev. Mr. Main, George C. Mallot, Alfred Parre, George Pulham, George Reid, William Robinson, J. P. Scharschmidt, J. C. Schraeder, Major A. E. Snyder, Rev. Mr. Stringer, Judge George L. Taylor, William Taylor, H. Wheeler, E. J. White, J. P. Whitney;' ; LOCAL COMMITTEE OF DAWSON, Y. T.-Hon. W.W. B. McInnes, Commissioner of the Yukon Territory, Honorary Chairman; Major Z. T, Wood, Assistant Commissioner of the Yukon Territory, Honorary Chairman; J. B. Tyrrell, Chairman; J. Moore Elmer, Vice-Chairman; George Black, Secretary; Hon. Mr. Justice Dugas, Hon. Mr. Justice Macaulay, Hon. Mr. Justice Craig, Dr. Alfred Thompson, D. A. Cameron,. E. W. Griffin. The first session, held in the ministers' room of the Parliament Building, 3 p.m., Saturday, July 1st, was presided over by Past-President Robert W. Hunt. His Excellency the Lieut.-

Nov 1, 1905

By C. J. Fleisch, C. P. Clingerman

THE recent installation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. THE FURNACE PROPER A few of the characteristic points and dimensions of the furnace proper are: [Hearth diameter 26 ft. o in. Bosh diameter 29 ft. 1 3/4 in. Stock-line diameter 20 ft. o in. Large-bell diameter 114 ft. 8 in. Small-bell diameter 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed 94 ft. 4 in. Height of furnace from center of iron notch to main platform 105 ft. o in.] The furnace top is equipped with a McKee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. g in. in diameter, then through uptakes that are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. DUST CATCHER The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catcher is g ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is 50° with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas in-

Jan 1, 1943

By R. P. Carreker, R. W. Guard

True stress-true strain data are given for nominally pure molybdenum (99.95 pct) over the temperature range -196° to 1540°C (0.027 to 0.63 T/T). Strain rate sensitivity was determined by rate change tests and stress relaxation tests. Inhomogeneous yielding and strain aging effects were observed. The yield stress and tensile strength depend markedly on temperature below 400°C and are insensitive to temperature in the range 400' to 800°C. The ductile to brittle transition range is +25O to -25OC. Strain rate sensitivity and stress relaxation effects are very large near room temperature. THIS report presents data which were obtained as a part of a continuing program designed to document the deformation behavior of nominally pure metals over a wide temperature range.'" This research program is rooted in the conviction that sufficient tensile and creep data of appropriate quality and detail does not exist to provide precise phe-nomenological descriptions of the deformation behavior of pure metals as a function of temperature, strain rate, and grain size. Such knowledge is needed to provide a firm base for alloy design and an experimental framework to which theories of deformation must conform. These data also complement a parallel exploratory program investigating the properties of refractory metals, including molybdenum, and their alloys. Several important reviews and research reports dealing with the tensile properties of molybdenum as a function of temperature have appeared."-lo To a great extent the work to be reported in the present paper parallels that of Bechtold and of Pugh. The authors' results are in general agreement with those of Bechtold and Pugh. The principle differences be- tween the present experiments and those published previously are as follows: 1—Wire specimens prepared from arc cast molybdenum were used in the present experiments, bar specimens were used by others. Pugh used arc cast material while Bechtold's most extensive results" were obtained on powder metallurgy specimens. 2—Several different grain sizes were tested in the present experiments. 3—The testing range was extended to cover from -196°C to 1570°C (0.027 to 0.63 T/Tm). 4—The combination of wire specimens, high speed autographic recording, and a stiff testing machine permitted more detailed study of initial yielding. The principle contribution of the present paper is the demonstration of the relatively consistent mechanical properties of nominally pure arc cast molybdenum specimens of differing metallurgical history. Bechtold and Scotts have shown that arc cast and powder metallurgy molybdenum samples have comparable tensile properties in the range —75" to 200°C when processed to have the same re-crystallized grain size. Material The molybdenum used in this investigation was supplied by the Climax Molybdenum CO. Its metallurgical history is outlined in Table I; the final products were 0,030 in, diam wire specimens annealed at 1100' and 1375°C and 0.060 in. diam wire

Jan 1, 1957

By F. Weinberg

In developing a mechanism for the solidification of metals from the melt, it has been proposed that solidification proceeds by the growth of platelets parallel to close packed planes. The evidence for this is based primarily on observations of decanted interfaces of lead1,2 and tin on which platelets 1 to 10 µ thick4 were observed. In recent observations of decanted eutectic alloys, 5,6 it was found that the eutectic structure on the decanted surface was markedly different than that of the bulk material, with the surface structure extending approximately 10 µ behind the interface.' This suggested that, at least for these experiments, a residual liquid layer 10 µ thick had been left on the decanted interface, which solidified subsequent to decanting. If a similar thickness of residual liquid was left on the decanted surfaces in the lead and tin observations referred to above, then it is questionable to what extent the observed platelets can be related to the solid-liquid interface before decanting. The purpose of the present investigation was to measure the thickness of the residual liquid layer on a decanted surface of tin, using relatively standard decanting procedures. The technique used was to add approximately 200 ppm of Tl204 (PI) to the melted portion of a high purity (99.999 pet) bar of tin, which was being progressively melted from one end, and then decant during melting. Since only the melt contained the radioactive tracer, the activity emanating from the decanted surface could be used as a measure of the thickness of the residual liquid layer. Progressive melting was carried out in the same fashion as single crystal growth, namely, in a horizontal graphite boat, in an argon atmosphere, using a moving furnace. The decanting was done in two ways; 1) removing the furnace and suddenly dropping the melt end of the boat, and 2) suddenly jerking the solid away from the liquid by the action of a falling weight (estimated peak acceleration 3 x 105 cm per sq sec), using a split graphite container. In all cases the melt was vigorously agitated by bubbling argon through it. The activity of the decanted surface was measured through an aperture 1.5 cm by 0.5 cm in a lead shield with an Anton tube geiger counter. Assuming that the active layer on the surface had the same concentration of Tl204 as the decanted liquid, the thickness of the layer could be determined from the measured activity of the decanted material, and the relationship between activity and material thickness. The latter was determined by rolling some of the decanted material into foil and measuring the activity of multiple layers of the foil. The activity At of material of thickness t (in mm) was determined to be A, = Ao(1 - e-22.5t) where Ao is the activity of the bulk material. The results of the measurements of the thickness of the residual liquid layer for six decants are given in Table I. The variation in t is attributed to variations in the decanting procedure and the rate of melting, the latter being difficult to control because of the vigorous agitation of the liquid. The rate of melting was in the order of 2 cm per hr, estimated from the position of the solid-liquid interface during melting. The results indicate that a residual liquid layer of the order of 10 µ in thickness is left on the decanted interface in agreement with the observation on eutectic alloys referred to above. If the mixing of the liquid during melting is not complete, as was

Jan 1, 1962

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By E. C. Reed

Ninety wells were completed in Nebraska during 1941, of which 42 were producers. One of them was the discovery well of a new field. All of the production to date is in Richardson County. At the close of the year 14 wells were drilling and three more were shut down for orders, hoping for future development of production. Most of the drilling activity was in Richardson County, which had 68 operations; 10 wells were drilled in Nemaha County, 5 drilled or drilling in Gage County, 3 each in Otoe and Furnas Counties, 2 each in Cass, Harlan, Johnson and Sarpy Counties, and 10 wells were completed or drilling over the remainder of the state. The most important development of the year was the discovery in October of the Barada field, sec. 36, T. 3 N., R. 16 E.,

Jan 1, 1942

By E. C. Reed

Ninety wells were completed in Nebraska during 1941, of which 42 were producers. One of them was the discovery well of a new field. All of the production to date is in Richardson County. At the close of the year 14 wells were drilling and three more were shut down for orders, hoping for future development of production. Most of the drilling activity was in Richardson County, which had 68 operations; 10 wells were drilled in Nemaha County, 5 drilled or drilling in Gage County, 3 each in Otoe and Furnas Counties, 2 each in Cass, Harlan, Johnson and Sarpy Counties, and 10 wells were completed or drilling over the remainder of the state. The most important development of the year was the discovery in October of the Barada field, sec. 36, T. 3 N., R. 16 E.,

Jan 1, 1942

By M. J. Hordon, M. A. Wright

The well-defined increase in fatigue life observed o many metals cyclicly strained at vacuum levels below 10-1 to 10-3 torr has been attributed to the critical retardation of oxygen or water vapor chemisorption at the crack tip during crack propagation.1-3 In the absence of strongly adsorbed surface films, crack re-welding during cyclic compression or dislocation escape from the plastic zone around the crack tip has been proposed to account for the observed decrease in the rate of crack growth. The increase in the critical pressure required for the transition in crack growth rate with temperature experimentally determined for aluminum was found to be generally in accord with the adsorption rate model.4 However, although the adsorption mechanism would also predict an increase in transition pressure and fatigue life with increase in cyclic loading rate, and such effects were noted by Snowden5 for lead and Hordon3 for aluminum, the opposite results were reported by Kramer et al.B in studies on aluminum. The present note describes some recent measurements of the fatigue properties of 1100-H14 aluminum at low pressures to determine the specific effect of cyclic strain frequency in the transition pressure range. Flat cantilever-type specimens of 1100-H14 aluminum shaped to produce a uniform strain gradient along the gage length were tested in reverse plane bending at constant deflection amplitudes in two independent multi-specimen vacuum fatigue systems. One series of tests using 2-in. gage length specimens was conducted in an ion pumped apparatus with 107 torr and 50 cps capacity, denoted as Unit I, utilizing fixed mechanical cams to impose the strain amplitude. An independent test series using shorter 1-in. gage length specimens was conducted in a cryopumped apparatus designed for extremely low pressures below 10-10 torr, denoted as Unit II, using an electromechanical vibrator at non-resonant frequencies up to 150 cps to provide the deflection. Both vacuum fatigue units and associated test procedures have been described previously.3&apos;7

Jan 1, 1969

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO&apos; afe aFeO &apos; aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K&apos;. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO&apos; afe aFeO &apos; aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K&apos;. Making these changes, 7

Jan 1, 1942

By David Mitchell

THE production of fluorspar is one of the smaller nonmetallic indus-tries in the United States with a capital investment-about $10,000,000. Shipments from United States mines&apos; in 1936 totaled 176,231 short tons valued at $3,111,268, an average price of $17.65 per ton. The United States produces about 40 per cent of the world&apos;s fluorspar, of which about 90 per cent comes from the Illinois and Kentucky deposits along the Ohio River.2 Further detailed information on the fluorspar industry in the United States is given by Hatmaker and Davis.28 Fluorspar is marketed according to the following relative quantities and specifications: Consump- Specifications, Per Cent Use Form tion in 1936, Per Cent CaF2 SiO2 Fe2O3 Metallurgical Gravel 79 +85 -5 or lump Ceramic,. Ground 10 +95 -3 -0,1 Acid Ground 11 +98 -1 The concentration of the coarser sizes presents relatively little diffi-culty, good recoveries being obtained with jigs and tables. However, sizes smaller than about 10 mesh cannot be successfully treated by ordinary gravity separation methods and so have been accumulating as

Jan 1, 1938

By David Mitchell

THE production of fluorspar is one of the smaller nonmetallic indus-tries in the United, States with a capital investment-about $10,000,000. Shipments from United States mines1 in 1936 totaled 176,231 short tons valued at $3,111,268, an average price of $17.65 per ton. The United States produces about 40 per cent of the world&apos;s fluorspar, of which about 90 per cent comes from the Illinois and Kentucky deposits along the Ohio River.2 Further detailed information on the fluorspar industry in the United States is given by Hatmaker and Davis.28 Fluorspar is marketed according to the following relative quantities and specifications: Consump- Specifications, Per Cent Use Form tion in 1936, Per Cent CaF2 SiO2 Fe2O3 Metallurgical Gravel 79 +85 -5 or lump Ceramic.. Ground 10 +95 -3 -0.1 Acid Ground 11 +98 -1 The concentration of the coarser sizes presents relatively little diffi-culty, good recoveries being obtained with jigs and tables. However, sizes smaller than about 10 mesh cannot be successfully treated by ordinary gravity separation methods and so have been accumulating as

Jan 1, 1938

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski&apos;s method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6&apos;7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6&apos;7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann&apos; suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in &apos;K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1&apos; values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941