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By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By J. Chipman, N. J. Grant, J. C. Fulton

This paper contains data on the distribution of silicon between liquid iron-silicon-carbon alloys saturated with respect to graphite and CaO-SiO2-Al2O3 slags under 1 atm of CO at 1600°C. The ranges of slag compositions studied were extended from the dicalcium silicate saturated liquidus composition up to silica concentrations at which Sic appeared as a stable phase. IN blast furnace operation it is not to be expected that slag and metal reach equilibrium with one another. Nevertheless, the silicon content of the metal varies with slag composition and with temperature in a manner which would be predicted from equilibrium considerations. Similarly, the distribution of sulphur between slag and metal does not attain an equilibrium state, yet the influence of slag composition is strongly analogous to its effect on the distribution equilibrium. The desulphurizing power of metallurgical slags has been shown to be highly dependent upon the FeO content of the slag. Moreover, the rate of removal of sulphur from slags is influenced by the oxygen potential of the slag-metal system. Thus it was shown by Grant, Kalling, and Chipman1 that the presence of MnO in slags which are low in FeO causes a marked slowing down of the transfer of sulphur from metal to slag. This led to the hypothesis that the slow removal of sulphur by blast furnace slags of more acid composition might be due in part to the effect of SiO2 on the oxygen potential of the system. This was verified in the work of Grant, Troili, and Chipman,' who found that the desulphurizing power of the more acid blast furnace slags could be markedly improved by an increase in the silicon content of the underlying metal. Their explanation of this improvement was that the higher silicon content of the metal decreased the rate of transfer of more silicon and, along with it, of oxygen from the slag to the metal. The slowness of the transfer of sulphur from metal to slag was the result of the slow reduction of SiO2 from slag to metal. Attempts to study the rate of sulphur removal had in the past resulted in very slow rates corresponding to the rates of silica reduction. It has become evident on the basis of these studies that further experimental studies on the rate of removal of sulphur must take these factors into consideration if there is to be a clear understanding of the rate of sulphur transfer under conditions simulating those existing in the blast furnace. It will be necessary, at least in a part of such study, to employ combinations of slag and metal in which the disturbing effect of silica reduction has been eliminated; in other words, to employ slag-metal combinations which are already in equilibrium with respect to the transfer of silicon. In preparation for such studies of desulphuriza-tion, a preliminary program of research on the distribution of silicon between slag and metal has been undertaken. This will ultimately include a comprehensive survey of the effects of temperature and slag composition on the equilibrium distribution of silicon between slag and metal. The present paper is a report on experimental methods employed and on

Jan 1, 1954

By D. B. Gillies

IN 1938 the Republic Steel Corp. announced that it had leased the ore mines and other property of the Witherbee Sherman Corp. at Port Henry, N. Y. The announcement brought forth an interesting reaction. Two questions were asked repeatedly: (1) Is the iron product high grade? (2) Is there a substantial reserve? The answer to both questions was and is a decided and emphatic "Yes."

Jan 1, 1943

The rich Tiller seam in southwest Virginia averages 10 to 15 ft in thickness. But because it is separated into two benches, mining engineers for years considered it neither physically nor economically feasible to mine. Profitable recovery of this coal has been made possible only by: full-seam mining with automatic machines; and the largest and most highly automated coal preparation plant of its kind-a plant ten stories high which washes, screens, and dries at the rate of 1500 tph, and produces both metallurgical and steam coal products. The Moss No. 3 preparation plant of Clinchfield Coal Co. Div. of Pittston Co. is located at Clinch- field, Va., only a short distance from the 450-tph Moss No. 2 plant, and was designed, built and erected by Link-Belt Co.

Jan 7, 1959

February 18th, 1873. THE Institute assembled in the Hall of the Boston Natural History Society on Tuesday evening. Dr. T. Sterry Hunt, of the Boston Institute of Technology, after a brief address of welcome to the Institute, read an introductory paper on the Geognostical History of the Metals. President Raymond responded to the welcome of Dr. Hunt. The following names were then presented to the Institute, with the recommendation of the Council, for election Adams, J. M., - Silver City, Idaho. Daggett, Ellsworth, - Salt Lake City, Utah. Geist, Alfred W., - Boston, Mass. Hays, Dr. S. Dana, - Boston, Mass. Heinrich, Oswald J., - Midlothian, Va. Johnson, J., - Braidwood, Ill. Leckie, Robert G., - Actonvale, Canada. Lyman, Edward, - Troy, N. Y. Maltby, William, - Braidwood, Ill. Nichols, Lyman, Jr., - Boston, Mass. Ordway, Prof. J. M., - Boston, Mass. Rand, Theodore D., - Philadelphia, Pa. Richards, Prof. Robert H., - Boston, Mass. Rockwell, Prof. Alfred P., - Boston, Mass. Roepper, Charles W., - Bethlehem, Pa. Schulz, A. von, - Central City, Colorado. Singer, William F., - Pittsburgh, Pa. Spillsbury, E. G., - New York. Wells, Calvin, - Pittsburgh, Pa. The session concluded with the reading and discussion of a paper, by Henry Engelmann, On the Mines and Ores of the Little Cottonwood Canyon, Utah. The second session was held on Wednesday morning, when the following papers were presented; On the Midlothian Coal Mines, by Oswald J. Heinrich. On the Probable Existence of Microscopic Diamonds in California, by Prof. Benjamin Silliman.

Jan 1, 1873

By Robert Mehl

IT is generally understood by workers in the field of the crystal struce ture of metallic alloys that terminal solid solutions are of two types, the substitutional and the interstitial. In reviewing the literature, the work of Weiss1 on the crystal structure of the alpha copper-tin alloys wa-encountered, in which a new type of terminal solid solution was proposed. In brief, Weiss' findings showed that the density of the alloys calculated from the side of the unit face-centered cube on the assumption of simple substitution-that is, with four atoms to the unit face-centered cell-was much higher than the density measured directly. It was suggested that the assumption of four atoms to the unit cube is not valid for these alloys, and that each unit cube contained less than four atoms; in other words, that one tin atom replaces more than one copper atom, leaving some atomic positions unoccupied. Such a structure, if verified, would have far-reaching significance in the study of the crystal structure of metallic alloys. It would indicate a complexity in terminal solid solutions not hitherto suspected and might encourage work leading to the discovery of other alloys of the same type, and perhaps to types intermediate between it and the two recognized types. It is of importance, therefore, to reinvestigate these alloys with respect to the type of solid-solution structure obtaining therein.

Jan 1, 1929

By Frank M. Randall

The Buick mill is located at the site of the old Buick general store, approximately 4 miles south of Bixby, Missouri on route KK. It is a part of the operations in the area now called the "New Lead Belt". The ore body lies at an elevation of 270 feet above sea level, and is fairly flat lying, becoming slightly deeper toward the south. The mineralization is due to the secondary deposition of galena, sphalerite, chalcopyrite, pyrite, calcite, dolomite and some localized drusy quartz in a country rock of dolomitic limestone. The galena is fairly coarse grained with some large crystaline structure, and some oxidized surfaces. The sphalerite is fine grained- small crystals containing Cd (about 0.7%) and Ag (about 10 oz per ton) in solid solution. The chalcopyrite is fine grained, fine crystals that are sometimes massive in nature. The mine plan is a modified room and pillar system. Broken ore at the mine face will be transported to several different ore passes by rubber tired load-haul-dump units. Ore passes will drop the ore to a rail haulage level some 90 feet below the mining level where bottom dump cars will deliver it to a 42 in. Nordberg gyratory crusher. Two 12 ton capacity skips in balance carry the ore some 1,200 feet to the surface. The hoist is equipped with automatic controls for loading, hoisting and unloading.

Jan 1, 1970

1. List of Manuscripts Seen in America 2. List of Manuscripts Seen in England 3. List of Maps Examined 4. List of Newspapers Examined 5. General Bibliography - Numbered Reference List

Jan 1, 1942

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961

By Leon W. Dupuy

SUPPLEMENT THESE tables should accompany Figs 6, 7, 8, 9 and 10, respectively. To follow Fig 6: TABLE 2[a]-Drill Rod [ ] To follow Fig 7: TABLE 3-Rod Coupling [ ]

Jan 1, 1947

By D. Foster Hewett

The scope of this paper is the description of two districts in Peru in which deposits of vanadium have been found, and the consideration of much laboratory-work that I and others have done to determine the nature of these deposits. It is with regret that I present some of the data in a state of evident incompletion, particularly the analyses of a few of the minerals, which leaves some doubt as to whether the true nature of the migerals is understood. I make no apology, however, since in this case, as in many others referring to ore-deposits, conclusive opinions cannot be stated until a great amount of work has been done, and the deposit has been thoroughly exploited. I believe that the data and the tentative conclusions here presented indicate a unique and interesting condition which may assist others in work along similar lines; arid further, what is of more practical importance, stimulate a search for a metal which, though long considered rare, is probably so merely because proper care has not been taken to recognize it. An excellent bibliography on the occurrence of vanadium in nature is given by I?. W. Clarke in his paper, Data of Geochemistry;' and in the preparation of this paper 1 have consulted many of the references contained in the Bibliography of the Chemistry of Vanadium, by M. Moisan.2 A brief review of the subject having special reference to the metallurgy of vanadium is contained in the small book by P. Nicolardot.3 One of these vanadium-deposits has already been briefly. 1 Bulletin No. 330, U. S. Geological Survey (1908). 2 Chimie Minerale, vol. iii. (1905). 3 Le Vanadium (1905).

Jan 1, 1910

By H. M. Howe, A. G. Levy

§ 1 Introduction.—This paper gives the results of our micro-graphic determinations of the position of Ae3 in a series of 14 hypo-eutectoid steels of varying carbon content, one of them very rich in phosphorus, and of SEe for one hyper-eutectoid steel. We have proceeded chiefly by noting the temperature at which the reabsorption of the pro-eutectoid element is found to be complete after a 30-min. holding, but in part also by noting the temperature at which its precipitation begins. Observations on these same steels by Messrs. Burgess, Crowe, and Rawdon, of the United States Bureau of Standards, are given in a paper1 issued simultaneously with this, while in a third paper2 one of us compares these data with those of earlier observers. These three papers are treated as one whole by numbering their sections, tables, and illustrations continuously, and by setting the folding plates of micrographs at the end of the last paper. The Composition of the Steels Experimented On is given in Table I. § 2. Notalion and Definitions.—Following Osmond's development of Tschernoff's notation, in which " Ac3 " is the upper limit of the hypo-eutectoid part of the transformation range as observed in heating up, and " Ar3 " is that same limit as observed in cooling down, and following the usual custom of calling the upper limit of the hyper-eutectoid part of that range " SE," we may go farther and call this latter limit " SEc" when observed in heating up and " SEr " when observed in cooling down. Further, we may call the equilibrium position of these lines, i. e., the position which they would have in pure iron-carbon alloys if all

Jan 1, 1914

By R. O. Day, R. S. Dean

In constructing a theory of the flow and hardening of metals, v necessarily make use of such phenomena as seem to be universal1 observed in metals. It is, therefore, a matter of concern to the con structors of such mnemonic systems if one or two of the group classific as metals show anomalous behavior. Such egregious phenomena observed in pure or nearly pure iron in the reaction of its mechanic properties to low-temperature annealing after cold work and to increase temperature of testing. In short it has been generally observcd tha iron, as an outstanding exception among metals, increases its hardnes and strength by low-temperature annealing after cold work,' and alt by increase of testing temperature to the range of 150" to 300" C. The investigation here recorded was made then with the object ( ascertaining if similar phenomena were observed in high-purity iro and, if not, to the presence of which impurities these phenomena coul be traced. Experimental Procedure Three kinds of iron were taken for a study of hardening by rehcatin after cold work: 1. Vacuum-melted electrolytic iron; melted in an Arsem furnace in a magnesia crucible. That this iron was of high purity is indicated b a magnetic permeability above 20,000. 2. Electrolytic iron melted in air in a small laboratory furnace. 3. Armco iron, commercial material. These materials in the form of forged bars, annealed at 980" C. in vacuum, were reduced 30 per cent. in thickness by cold rolling and the reheated to temperatures varying from 100' to 500' C. The Rockwe hardness number was measured after each treatment. The results and shown in Fig. 1, curves 1, 2 and 3.

Jan 1, 1929

By F. W. Luerssen, J. F. Elliott

F LUSHING the early slag from a stationary open Fhearth having a high percentage of hot metal in its charge is necessary in order to remove silica from the system. The flush slag is strongly oxidizing and is somewhat acidic. It has, however, considerable capacity to extract phosphorus from the bath and it also removes considerable manganese. It seems probable that factors which control the distribution of phosphorus and manganese between slag and metal in the refining period also should be dominant in the flush and postflush periods. Several studies, as summarized elsewhere,1,2 support the viewpoint that conditions closely approaching equilibrium for these elements are rather readily established during the refining period. Over the years these studies have repeatedly demonstrated that 1—high slag v01ume, 2—low bath and slag temperature, 3—basic slag, and 4—strongly oxidizing slag favor rapid elimination of phosphorus from the bath to the slag. They also show that the following conditions favor retention of manganese in the bath: 1—low slag volume, 2—high bath and slag temperature, 3— basic slag, and 4—minimum oxidizing power of slag. When it is considered that the flush slag often carries as high as 75 pct of the manganese charged and only 25 to 60 pct of the phosphorus charged, it is evident that in removing silica much manganese is sacrificed but phosphorus removal is far from conplete. Because of overriding circumstances, this is accepted in most operations and actually it is considered to be inevitable. This may account for the fact that little attention has been paid to conditions affecting the elimination of phosphorus and manganese in the flush slag. A recent study of the behavior of various charge oxides has developed considerable information on the flush and postflush periods. Because the data are felt to be of general interest, they have been brought together and Presented in this paper. The object is to show the various factors in the flush and postflush periods which influence elimination of phosphorus and manganese. Physical Conditions During and After Flushing Physical conditions existing during the flush vary from plant to plant, from shop to shop, from furnace to furnace, and even from heat to heat. They are strongly influenced by the physical and chemical character of the charge oxide which is ordinarily necessary to provide sufficient oxidizing power early in the heat. Invariably the period is characterized by a vigorous reaction between the principal re-actants: the hot metal being added and the charge oxide. During the flush, it is probable that the slag acts to some extent as an oxidizer; but, because of the critical influence of the behavior of the charge oxid'e on flushing action, it seems apparent that the oxide itself is the dominant oxidizer. Fig. 1 shows the course of two heats which were selected as being typical of the group studied. Heat A was charged with 55 pet hot metal, based on the total metallics charged, and heat B had 57 pct hot metal. As indicated in Table I and Fig. 1, the melt-down slag, which is not usually voluminous and which is principally FeO, expands greatly in volume and will show rather high levels of SiO2, MnO, and P2O5 very soon after the beginning of the hot metal addition. Simultaneously, large volumes of CO are liberated which cause violent mixing of slag and metal. It is of interest to note that the time required to bring carbon down to a low level is very much longer than that required for the removal of silicon, manganese, or phosphorus. At the end of flush, carbon in the bath is still approximately 2 pct. When strongly reducing hot metal is brought into contact with strongly oxidizing conditions within the furnace! it is probable that the rate of mass transfer to the slag (and atmosphere) of silicon, manganese, phosphorus, and carbon initially depends principally on the rates at which the two participating phases are brought into contact That is, it depends on the nature of the various reactions. Later in the flush period, when the scrap is virtually all dissolved and the action of the bath has settled down to a steady and somewhat gentle boil, it is likely that other factors, such as the transfer of oxygen across the slag-metal interface, become dominant. The temperature of the slag-metal system is far from uniform. Heat is being driven by the flame down through the slag. Bubbling and surging of the metal also frequently brings portions of the bath in contact with the flame. At areas of contact between the ore and liquid metal, or slag and liquid metal, the oxidizing reactions generate much heat. On the other hand, scrap is being melted which tends to absorb large quantities of heat. Because the liquid bath is high in carbon, the steel scrap is brought into solution rapidly. This can proceed at a rather low temperature; and until much of the scrap has been taken into solution, the bath temperature would not be expected to increase appreciably. Consideration of these factors leads to the conclusion that during the flush period the slag should be rather hot and the bath relatively cold. Both observation and temperature measurements bear this out. Experimental Data The extended program of charge oxide evaluation permitted study of the widely varying conditions existing during the flushing period. Slag and metal analyses and bath temperatures reported herein (Tables I and 11) were obtained toward the latter portion of the work. Four different types of charge oxide, sinter, two types of hydraulic cement-bonded soft ores, and a pyrobonded agglomerate were used in the study. Although the heats reported were from only one 205 ton furnace, they show variations in flush slag analyses all the way from 25 pct FeO, which is typical with the use of a hard natural charge ore, to 45 pct FeO which resulted when a very poorly agglomerated fine ore was used. The physical behavior of the flushes showed a correspondingly wide variation from well controlled reactions to violent surges following periods of inac-

Jan 1, 1956

By C. G. McLachlan

This paper outlines a series of tests carried out during the first six months of 1927, in the laboratory and mill of the Moctezuma Copper Co. The object of the tests was to determine whether the soluble salts present in the mill circuit water were having a detrimental cffect on the recovery made by flotation. To accomplish this object a series of water analyses were made, followed by flotation experiments in which definite quantities of the salts found were added as addition agents. Before proceeding to describe the results obtained in the course of the investigation, reference will be made to five articles that have appeared during the last two years in which the action of such salts is discussed. Two of these are by A. T. Tye1, 2 and describe flotation practice at Cananea and the way in which water high in ferrous and ferric salts is conditioned for differential flotation. Two, one by A. C. Munro and H. A. Pearse3 and the other by H. A. Pearse,4 outline Britannia milling methods, and the advantages that have been derived from ore washing; while in the fifth, A. W. Hahn5 summarizes the results of laboratory experiments in which ferrous, ferric and aluminum sulfates have been added in varying amounts. The mill of the Moctezuma Copper Co. has a daily capacity of 3000 tons, and is situated about 75 miles south of Douglas, Arizona, on the Rio de Nacozari, in the Mexican state of Sonora. The ore treated is mined from the company's mine at Pilares, about 5 miles southeast of the Concentrator. This ore contains about 2.5 per cent. copper— present almost entirely as chalcopyrite—and 10 per cent. iron, of which

Jan 1, 1928