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By B. M. Larsen

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

Jan 1, 1941

By B. M. Larsen

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

Jan 1, 1941

By D. J. Pye

Certain high molecular weight synthetic polymers in very dilute solutions decrease water mobility in porous media 5 to 20 times more than would be expected from the solution viscosity. This indicates that increasing water viscosity to reduce adverse mobility ratios in water floods is economically feasible in many situations. Laboratory results are consistent with accepted theory with respect to improved areal sweep, permeability distribution and displacement efficiencies as would be predicted from the solution mobility measured in the core. The laboratory results have been confirmed by field pilot floods which recovered 80 per cent and 100 per cent more oil than comparative water-flood pilots in fields containing 16 cp and 130 cp oil respectively. Economic analyses based on pilot data indicate the method to be profitable. INTRODUCTION The desirability of improving the water-oil mobility ratio in waterflood-ing operations has long been appreciated, especially for high viscosity crudes. Methods of reducing the oil viscosity by application of heat, gas resaturation and miscible drives have met with some success. Conversely, it has been generally conceded that increasing the water viscosity would also be effective, but the amount of thickening agent required to effect an appreciable increase in viscosity is discouragingly high. The use of such materials as glycerin, sugar, or glycols is completely out of the question economically, so that considerable attention has been given to the use of the much more efficient synthetic water-soluble polymers as viscosity improvers; but even these materials are not economically attractive. If increased water viscosity could be economically realized, marked improvements in areal sweep efficiency, as discussed by Caudle and Wittel and others, would be realized in field operations. Similarly, the improved mobility ratio would bring about increased recoveries by correcting permeability distribution problems as discussed by Stiles2 and Dykstra and Parsons,' and improvements in displacement efficiency would be obtained as recognized by Buckley and Leverett4 and Welge.5 LABORATORY STUDIES THE RESISTANCE EFFECT In the course of research to develop a more efficient water-soluble polymer viscosity builder, we discovered that a very few types of water-soluble polymers exhibited a most unusual and very interesting property not previously observed. Among the earliest materials showing such activity were polymers containing acry-lamide. Fig. 1 shows a typical plot of the solution viscosity vs concentration for one of these polymer solutions as determined in an Ostwald viscometer. As usual, such a plot is an approximate straight line on semi-logarithmic paper. Now, an inspection of Darcy's law, shows that a viscosity value can also be determined in a formation sample if the pressure, flow rate and permeability are known. If the core permeability is previously determined with wa- ter or brine, then the viscosity of another aqueous fluid may be determined from the equation. The viscosities so determined for glycerin (glycol or polyvinyl alcohol solutions, for example) agree with the viscometer determinations. However, in the case of the water-soluble polymer solutions in which we are interested, the viscosities measured in the formation sample depart very markedly from the viscometer values. A typical relationship for a polymer solution is also shown in Fig. 1. This unusual departure from the expected response is referred to as a resistance property of the polymer and is quantified as "resistance factor". Since the resistance factor R can best be determined in a core under study, the term has been defined on the basis of the ratio of the brine mobility to the polymer solution mobility at residual oil saturation so that:

Jan 1, 1965

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By E. T. Dumble

(San Francisco Meeting, September, 1915) THE history of the several petroleum deposits of Texas and Mexico, or of the sediments in which they now occur, if the deposits are not indigenous to such sediments, is known in a general way only, but it nevertheless casts strong light on the conditions surrounding them and is of great importance in the search for and exploitation of then. The petroleum deposits of Texas are separable into two main divisions: 1. The deposits of northwestern Texas, which are directly connected with the Oklahoma fields to the north, and have no representatives at all in the Mexican area. 2. The deposits of the coastal area, which extend into Louisiana on the east and connect with those of the Mexican coast to the south. Early in the Pennsylvanian period a series of bituminous shales and limestones were laid crown over a broad area in Texas, Arkansas, and Oklahoma. These are known as the Bend series in Texas, the Caney shales in Oklahoma, and the Fayetteville beds in Arkansas. Following their deposition an uplift occurred, forming the Lampasas geanticlinal, which runs northeastward from the old Paleozoic land area of the Llano region toward Red River. The Bend series is petroliferous in places and has furnished a few producing wells on each side of the Lampasas uplift. This uplift forms the barrier and. dividing line between the two divisions of the Texas petroleum deposits. To the west of it, in waters which were the southern extension of the interior continental seas, in connection with the sediments and coal beds of the Pennsylvanian and Permian, great quantities of petroleum were deposited either as oil or as "potential petroleum." These sediments have been subject to very slight disturbance, and only very gentle folds. are found, with no signs of volcanic action in any part of the area. The conditions, therefore, indicate that the greater part, if not all, of the oil in this area is indigenous to the beds in which it is found.

Jan 8, 1915

By F. S. Sinnatt

THIS paper is the outcome of an extended investigation carried out in association with Dr. L. Slater. The inquiry had been continued in various directions and a number of results are quoted from an investigation recently completed by S. H. Jenkins. In projecting the work some five years ago, the author had in view a general attack on the problem of the spontaneous combustion of coal from an angle that had received little attention. The basic idea was to obtain a "slow motion study" of the active combustion of coal. This included an examination of the conditions prevailing in a mass of coal at the moment when active combustion ceases. It was thought that, if the factors governing the extinction of combustion in coal could be definitely established, it might offer an explanation of the manner in which the spontaneous combustion of coal originates. The inquiry arose from a detailed study of the properties of fusain that the author began in 1918. Fusain seemed to possess characteristics quite distinct from the coal with which it was associated, for if it were collected into a heap and one portion were heated by a small flame the combustion would traverse the whole mass. This combustion was not accompanied by smoke and passed slowly through the heap of material. Later, it was found that coals, including anthracites, would behave in a similar manner provided they were in the form of powder and that the particles were smaller than a certain size. The limiting size of particles is a definite characteristic of the coals investigated. In view of the fact that fusain exists with coal in a state that enables it to undergo this particular form of combustion, it must be assumed, sometimes, to playa definite part in the spontaneous combustion of coal in the goaf (waste).

Jan 3, 1925

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

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

Jan 1, 1945

By G. F. Loughlin

The subject of this lecture might well have been assigned to an economist or banker rather than to a geologist, but, as it was deliberately assigned to me, it is to be treated from a geologist's viewpoint. The term precious metals ordinarily includes the platinum group as well as gold and silver. Platinum, like silver, has had a great decline in price during the last few years, but has not been a medium of exchange and therefore has aroused comparatively little comment. Its relation to price level is like that of commodities in general, and will be dismissed without further comment. Of the two precious metals used as mediums of exchange gold, because of its adoption as the basis of most monetary systems and because of its threatened shortage in the near future; has been a subject of general concern to governments, financiers, and economists; silver, on the other hand, which has flooded the market of late has brought forth cries for help, direct or indirect, from producers and to a less extent from the largest users, especially China, whose purchasing power has been greatly curtailed, but it fails to arouse the interest that gold does. Many predictions have been made by economists, bankers, and others regarding future supply of gold and its effect on prices but the differences among these predictions are about as many as the number of prophets. Since gold is the standard by which the value of commodities as a whole is to be measured, it would seem that the greater the ratio of gold supply to commodities the higher the price level and vice

Jan 1, 1932

By J. M. Callow

HISTORICAL SKETCH THE selective action of oils for lustrous minerals was first disclosed by Haynes in 1860. In 1885, Miss Carrie Everson elaborated this idea and also disclosed the fact that acid increased the. so-called selective action. Her patent called for oils, either animal, vegetable or mineral, also for an acid or salt. The process was tried out on a practical scale in Baker City and Leadville, in 1889, and failed: first, because,, as has since been shown, of the unsuitability of the ore to flotation; and second, because the invention was too far in advance of the times. Then followed the Elmore brothers, first with their bulk oil processes and later with their vacuum method. The basic principles of oil flotation were undoubtedly covered by the above inventors, the work done since their time being merely a building up on ground work laid by them. Different kinds of oil, different quantities of oil, and all the varying degrees of agitation, were all exemplified and practiced by them in one phase or another, and the developments that have since been made are but elaborations of the fundamental principles laid down by Haynes, Everson, and the Elmore brothers. In 1902, the Potter-Delprat process was developed in Australia. In this process no oil was used, the mineral being raised by the generation of gas, brought about by the introduction of acid into the pulp. The mineral particles appeared on the surface of the separatory vessel, in the form of a scum or froth, buoyed up-by minute gas bubbles attached to them. This no doubt first gave the suggestion of gaseous flotation. In 1902, also, Fromont, an Italian, was granted a patent in which. he combined violent agitation with oil and gaseous flotation, the gas being generated within the pulp, in much the same way as in the Potter-Delprat process.

Jan 12, 1915

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half'-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.'' The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By Wayne D. Gould, Terry O. Arney

The Pinto Valley digital control system is a supervisory system interfaced with a conventional analog control system. The design criteria, the hardware selection, and the startup of the system in the Pinto Valley concentrator are reported in depth. Examples of data collection application, as well as the present and immediate future implementation of control strategies, are discussed. This paper is a description of the digital data acquisition and control system that is installed at Cities Service's Pinto Valley concentrator.

Jan 1, 1978

By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and ' steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation' concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.' Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

By Joseph H. Allen

In the old Kentucky reports, made by the Survey of which Prof. Owen was director, the veins of the Western Kentucky coal-field were numbered from 1 up to 12. Later Prof. Shaler used letters, beginning at the top. For instance, Owen's 12 is Shaler's A.

Jan 1, 1888

By J. Chipman, M. N. Dastur

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

Jan 1, 1950

By H. H. Rachford, D. W. Peaceman

A system of partial differential equations describing miscible displacement of fluids in porous media is derived The system takes into account the influence of gravity, the spatial distribution of permeability, diffusion, and fluid viscosities and densities. A numerical procedure for approximating solutions to the differential systems has been tested for a horizontal two-dimensional geometry. In end-to-end displacements of oil with less-viscous solvents, the numerical solutions exhibited fingering qualitatively similar to that observed in laboratory models. Small random spatial variations in permeability about the mean value are sufficient to initiate fingering. Quantitative comparisons of computed results with laboratory data show good agreement. INTRODUCTION Miscible flooding of oil by solvent is receiving increasing consideration for field use.1-4 Unfortunately, such floods potentially present severe problems in loss of recovery through the by-passing of oil by expensive solvent. Consequently, their economic evaluation requires sound techniques for predicting recovery. The purposes of this work are to present a finite-difference method for calculating the multidimensional displacement of oil by solvent and to investigate the validity of the method by comparing results of calculations with data from displacements in laboratory models.5 The formulation of the method to simulate the model experiments treats a case of limited scope in the description of solvent flooding in the reservoir. The model experiments were carried out with fluids that were assumed to form an incompressible, ideal, two-component system with constant diffusivity. Establishing the validity of the method even in its present form provides a major step toward the goal of quantitatively evaluating individual solvent flooding projects. First, it demonstrates the fea- sibility of calculating the course of displacements which are dominated by an inherent macroscopic instability, i.e., viscous fingering. In addition, the method provides almost the only practical means of examining the effect of the size and extent of reservoir inhomogeneities on the development and propagation of the fingers, taking into account the important influences of diffusion and gravitational segregation. It might be inferred that such studies cannot yield results of practical value because in displacements dominated by macroscopic instability the pattern of finger development and the resulting performance should depend critically on small variations in the geometric distribution of reservoir inhomogeneities. The present method offers the capability inherent in computational techniques of predicting performance reproducibly with any arbitrary distribution of reservoir properties and, as such, provides a means of evaluating the sensitivity of behavior to uncertainties in reservoir definition and, thus, assessing the reliability of prediction of performance. THE PHYSICAL PROBLEM DATA USED FOR QUANTITATIVE TESTS OF CALCULATIONS In this work, a calculation for treating the miscible-displacement process is tested by comparing calculated results with experimental data. The experiments chosen for comparison have been described in detail,5 and the quantitative features are summarized in a later section. Briefly, oil was flooded by solvent of equal density from a thin rectangular channel in Lucite packed with uniform Ottawa sand. Under these conditions, two-dimensional geometry is considered adequate to represent the process. Inasmuch as the present work is concerned with testing of the method by comparison with specific two-dimensional data, the system of equations presented in the succeeding section will be oriented to defining the physical system specifically. THE DIFFERENTIAL EQUATIONS Suppose x, y to be a Cartesian co-ordinate system and define h(x, y) to be the height of a point above a horizontal reference plane. It will be assumed

Discussion of the paper of G. K. Burgess and J. J. Crowe, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2537 to 2591. HENRY M. Howe, New York, N. Y. :-I think we can hardly rate the importance of the entry of the Bureau of Standards into our field. There is no body in the world that is better fitted to undertake this work than that Bureau, and it is work which really calls for the aid of some national organization. The skill and care with which this work has been done speaks for itself. It is very striking that within a very few months the distinguished English investigator, Professor Carpenter, of whom I spoke before, thought that he had disproved the existence of beta iron by proving that the A2 retardation which Professor Burgess has now demonstrated did not occur. Dr. Burgess's demonstration of the existence of. this retardation makes the existence of beta iron very probable, in my opinion. Osmond used to call beta iron " decipuum." You knew of its existence as you know of the existence of certain planets, only by the perturbation which it caused. Certain phenomena could not be explained, except by assuming the existence of a third allotropic form, beta iron. The evidence that you got was always evasive and susceptible of other explanations, except that which we have to-day, which it seems to me is not capable of other explanation. Professor Carpenter proceeded in the same way that Dr. Burgess has, by taking the heating and cooling curves of exceedingly pure iron, and thought that he had shown that there was no thermal change, no absorption or evolution of heat at the supposed A2 point, and hence that the A2 point did not exist. This he did by a piece of reasoning which I think seems to most of us rather surprising. That is to say, if of ten witnesses, three have seen a thing and seven have not, the evidence of the seven who have not is set aside, and that of the three who have seen stands. In Dr. Carpenter's own experiments under certain conditions he found the A2 change, the heat evolution., under certain others he did not. That is like the three witnesses who saw and the seven who did not see. You can arrange your test so that this change will not become visible or so that it is masked. But though an existent change can be masked a non-existent one cannot be shown. So that the reasoning seemed to me wholly fallacious.

Jan 12, 1913

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By Carl E. Swartz

Although a number of articles appeared during the war advocating the use of cadmium in lead-tin solders, very little information of value can be found in the literature regarding the properties of solders containing cadmium. In most of the published articles the cadmium seems to have been considered merely as a partial substitute for tin in a tin-lead alloy rather than as an essential constituent of a ternary alloy. The primary object of the substitution of cadmium for tin was to lessen the amount of tin required, at a time when the latter was scarce and high-priced, and thus to produce a cheaper solder. While this object was accomplished, the new properties resulting from a change from a binary lead-tin alloy to a ternary lead-tin-cadmium alloy were not given proper consideration in many cases. For the past few years, the American Smelting & Refining Co. has been marketing a very considerable amount of cadmium in the form of lead-tin-cadmium alloys for use as solders for certain special purposes, and the successful use of these solders suggested that if more extensive knowledge were available concerning the properties of lead-tin-cadmium alloys of various compositions their field of usefulness might be materially extended. The investigation described in the present paper was undertaken to obtain this information and, by means of tests under conditions approaching those of practical use, to determine the suitability of cadmium solders for various purposes. Characteristics and Requirements of Solders in General General Physical Properties.—When cast into bars, solder should present a smooth and bright appearance free from oxide inclusions and bubbles. Ductility should be as great as possible without sacrificing tensile strength, and vice versa. Hardness and specific gravity are not of any great importance. Melting Characteristics.—The melting or solidification range is important. This statement applies both to the extent of the range and to the actual temperature at which complete solidification occurs. A rather narrow solidification range is desirable in soft solders in order that solidification may take place quickly. The solder should have high fluidity at temperatures only slightly above its melting range. For a

By W. E. Curran

For years the geographical isolation of the Southern iron-ore district from the great producing centers in the North and East enabled it to meet its conditions and solve its own problems without regard to the practices and policies of other districts, but during the past few years distances have been shortened, practices and wages are being standardized, and these changing conditions have brought new problems to the South. Development of Pig Iron in the South The development of the pig-iron business in the South was very slow during its early years, gained speed rapidly in the latter part of the nineteenth century, reached its peak in 1918 and was on the decline before the depression that began in the latter part of 1929. The first blast furnace in Alabama was built at Cedar Creek in 1818, the year before the state was admitted to the union. In 1830, Daniel Hillman was sent from Tuscaloosa to found an iron works in Roupes Valley, where rich pockets of brown ore were numerous. He built a forge on the site of what later became Tannehill furnace and called it the Roupes Valley Iron Works. There pots, pans, plows, and horseshoes were made of metal from his Catalon forge; shaped by a large hammer operated by water power. Daniel Hillman died in 1832 and the ironworks lay idle until 1836, when Col. Ninion Tannehill bought the property, rebuilt the forge and, using slave labor from his plantation, operated and enlarged the works. By 1845 he had built two crude furnaces and did a flourishing business in ovens, skillets and kettles, which found a good market all over the South. In 1855, the plant was sold by Colonel Tannehill to Moses Stroup, an experienced ironmaster from Pennsylvania. He tore down the old furnaces and built a new plant, the ruins of which stand today (Fig. l). This furnace plant operated continuously until it was destroyed by Northern troops in 1865. It was never rebuilt, so that the shell in the picture is the same furnace that made many tons of guns and shells for the Confederacy during the war period.

Jan 1, 1938

By Joseph E. Pogue

In 1920, 531 million barrels of crude petroleum were coi~sumed in the United States. As imposing as this figure is, the fact that the domestic consumption of crude petroleum has increased at an average rate of 10 per cent. a year for the past decade is more striking. Will this rate of increase in demand continue? If so, the year 1930 will call for 1260 million barrels of petroleum—a staggering volume. On the other hand, may we expect the demand for petroleum to grow as rapidly as it did when the automotive industry was having its most phenomenal expansion? If not, to what extent will the growth of oil requirements decrease? When and to what degree will the petroleum industry become affected by the economic law of diminishing returns? Obviously, this matter requires careful analysis, especially as both national and industrial planning must be predicated upon present estimates of the requirements of the future. The purpose of this paper, accordingly, is to project, as closely as present limitations of knowledge permit, the course of the demand for petroleum in the United States over the next ten years. At first, the problem of estimating the future of a demand as complex as that for petroleum might appear insoluble. Fortunately, hon~ever, therc are several scientific methods of approaching the problem, centering around a study of rates of industrial growth, which lend considerable hope that the requirements of the immediate future in this field may be approximated with sufficient closeness to have practical value as a basis of action. Growth oF Petroleum Demand The demand for crude petroleum is the resultant of the demands for the products made jointly from this substance—gasoline, kerosene, gas and fuel oil, and lubricating oils. The demands for these have grown at

Jan 1, 1923