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By Harold Markus, Arthur H. Grobe, Gerhard Derge

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Frederic Lahee

THE total production of crude oil in Texas during 1924 was said to be 133,613,985 bbl. as compared with 125,991,628 bbl. in 1923.1 Subtracting from these figures the yield of the Gulf Coast fields, there remains, for the other part. of Texas, a yield of 106,272,573 bbl. in 1924, as compared with 101,931,595 bbl. in 1923. This represents an increased, production of over 4,250,000 bbl. for all of Texas outside of the Gulf Coast or Salt Dome fields. Within this same region, in 1924, there were 3624 completions, of which 2352 were oil or oil and gas wells, 7 were gassers, and 1265 were dry holes. Thus, nearly 35 per cent. of the completions were dry holes. In 1923, there were 4134 completions, with 2853 oil or oil and gas wells, 2 gas wells, and 1279, or 31 per cent. of the total, dry holes. Outside of the Gulf Coast region, six major pools were discovered and developed in 1924.; two pools, previously discovered, were extended far beyond their limits at the end of 1923, and many smaller pools were opened. The major pools were the Big Lake field, in Reagan Co., the New Richland field, in Navarro Co., the Harmel, Carey, and Ragle pools, in south Archer County, and the Wortham field, in Freestone and Limestone Counties. Fields that were notably extended were the Panhandle producing area and the Luling field. Many wildcat wells have been drilled; most -of these were failures, but several opened .pools and several have had sufficiently favorable results to. lead to further drilling. The activity of the operators in searching for new production was very intense during 1924, and indications point to as feverish a campaign during the coming year. This will be stimulated by rising prices for crude oil. There are good reasons for believing that new pools will be discovered along the Mexia fault zone, in Archer, Young, Baylor, and Throckmorton Counties, in the great central region of Texas where we now have the Mitchell County and Reagan County pools, and very likely in the eastern Red River Counties including Cooke and Grayson. On the other hand, with the opening of the year, there is no new big pool in sight. An outstanding feature of the production end of the business is the increasing reliance placed on geological work and geological recommendations. Not in five or six years has there been such a demand for first-class geologists.

Jan 3, 1925

By Arthur L. Christenson, Clarence E. Jackson

IN the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition1 may be corrected to the grain size observed in an actual weld,2 or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.3 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2100°F. has been used. In studies of the end-quench hardenability specimen quenched from 2100°F. instead of from a lower temperature of 1700°F., it is important to ascertain the relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6,7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been proposed: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching. temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1943

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By A. J. Shaler, J. Prieto Isaza, J. Wulff

Tantalum metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involwing high temperatures in vacuo some of the refractory metals 6ecome brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element colum-bium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum-columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen-containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides; one of the authors undertook4 an investigation of the thermochemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exo-thermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the Drocess should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonly made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tanta-

Jan 1, 1949

By J. R. Kyte, R. L. Dalton, V. O. Naumann, R. L. Ridings, R. W. Greene

This paper presents a one-dimensional numerical method for calculating dissolved-gas-drive behavior for a single well or a linear reservoir. Pressure and saturation distributions can be calculated, including the effects of capillary and gravity forces. The analysis has been programmed for solution on the IBM 7090 digital computer. A comparison of experimental and calculated behavior for two linear models demonstrates that the method is suitable for calculating dissolved-gas-drive behavior under reservoir conditions of flow. Dissolved-gas-drive tests were run, at different production rates and with oils of different viscosities, on short (6.ft) and long (173ft) flow models. For tests approximating reservoir pressure gradients and flow rates, there was excellent agreement between experimental and calculated results. A series of calculations of well behavior for thin, horizontal, homogeneous, dissolved-gas-drive reservoirs shows that ultimate recovery is independent of production rate or well spacing in such cases. These calculations also show that Muskat's method and similar material-balance analyses are not applicable under some conditions particularly for high pressure drawdowns. INTRODUCTION The problem of calculating dissolved-gas-drive reservoir performance has received a great deal of attention throughout the oil-producing indusfry for many years. Really significant advances, however, have been made only in recent years. The rapid evolution of high-speed computing equipment and techniques has opened up new approaches to the problem and led to realistic, quantitative analyses free of many of the assumptions and limitations of earlier methods. The one-dimensional numerical method described in this paper includes the effects of both gravity and capillary forces. A number of test calculations, based on different rates, spacings, and rock and fluid properties, have shown that the method is adequate for systems that can be reasonably represented by a one-dimensional model (linear or radial) and in which fluid segregation perpendicular to the direction of flow is not important. Along with the development of mathematical methods, an experimental program was conducted and the data were used to test the validity of the theoretical basis of the mathematical method. Linear models were used and all experiments were run using 1,000-psig bubble-point oils. The use of long, high-pressure models enabled us to more closely approach reservoir gradients and flow rates. MATHEMATICAL FORMULATION DIFFERENTIAL EQUATIONS The differential equations describing dissolved-gas-drive behavior in one dimension dare summarized here. They include Darcy's law for flow of oil and gas (Eqs. 1 and 2) and the equations for conservation of mass for oil and gas (Eqs. 3 and 4). The oil and gas pressures are related by capillary pressure (Eq. 51.

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, ' for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

By R. D. Barer, M. B. Bever

Age hardening alloys are quenched from the solution treatment to room temperature in order to retain a supersaturated solid solution. Some alloys age "naturally" in this condition but in most alloys aging is induced "artificially" by heating to intermediate temperatures. Cold working of the supersaturated solid solution accelerates the aging process and quenching strains have the same effect. The investigation reported here is a study of the progress of aging in specimens quenched directly from the solution treatment to various aging temperatures. This procedure reduces the temperature interval of quenching and the resulting quenching stresses. It also eliminates any changes which would take place in the undercooled sample at room temperature prior to aging at an elevated temperature. Isothermal aging is thus approached and its kinetics may be studied. An aluminum-copper and an aluminum-silicon alloy were chosen for this investigation. The aging mechanism of aluminum-copper alloys is complex while the aging of aluminum-silicon alloys is nearly ideal. As standards of comparison for the samples directly quenched to the aging temperature, specimens were also age hardened by the usual procedure in which solution treated samples are first quenched to room temperature and then reheated to the aging temperature. Review of Previous Work The mechanism of age hardening has been the subject of a controversy which has ranged from the theory of outright precipitation of an equilibrium phase to theories based on subtle changes occurring in the matrix prior to precipitation. A detailed critical review of the literature up to 1939 is available1 and contributions to the general theory of age hardening continue to be made.2,3 Age hardening, whatever its mechanism, involves the nucleation of a second phase within a supersaturated solid solution. Theoretical considerations4,5 indicate that the rate of nucleation reaches a maximum at an intermediate temperature below the temperature at which supersaturation sets in. Studies of precipitation at various subcritical temperatures have demonstrated that the largest property changes in a given time occur at such intermediate temperatures.6,7,8 The precipitation of a phase from supersaturated solid solution is accelerated by strains which may result from quenching or cold work. Phillips and Brick9 established that quenching strains are an essential condition for the age hardening of aluminum-copper alloys at room temperature, at least for aging periods of less than 30 days. They also found that on aging at 300°C the hardness increased faster and reached a higher maximum after quenching into water than after quenching directly to the aging temperatures. Fink and Smith10 observed preferential precipitation on slip bands and grain boundaries in aluminum-

Jan 1, 1950

By Wallace F. Lovejoy

The conservation of mineral resources as a public policy question has received a great deal of attention in the area of petroleum and practically no attention in other mineral areas, except, of course, soil and water. Some insights into mineral conservation problems and how these problems can be approached in the social decision-making process are significant. THE MEANINGS OF CONSERVATION Conservation means many things to many people .2, 11 Too often it is a label attached to a proposed program or policy to add respectability and to gain public acceptance. It is a term applied to specific resources in some contexts and to resources generally in other contexts. The oft-quoted comment of President William Howard Taft that conservation is something everybody is for, no matter what it means, succinctly illustrates the confusion over both the meaning of the concept and the policies required to implement a conservation program. This confusion goes quite deep and is more than a matter of semantics or emphasis. For example, the efficient exploitation of a mineral deposit which might be applauded as good conservation in terms of that mineral, might well result in destruction of or harm to the environment which might be viewed as bad conservation. Economics provides some tools to help solve this sort of problem, but there may be fundamental differences in value systems among groups in this society, so that ultimately society must collectively make a subjective political choice as to what is good or bad conservation policy.a An Economic Definition of Conservation The economic concepts of conservation have more relevance and are more easily applied to minerals than to many other natural resources. This does not mean that economics goes all the way in understanding mineral conservation, but at least it provides a framework for analysis which later can be altered to include noneconomic variables. Perhaps the greatest confusion in discussing mineral conservation arises in attempting to relate purely physical concepts with economic concepts. An economist is interested in maximizing or conserving values; he is not interested in maximum physical recovery or utilization. He wants to know the costs and benefits of using, or not using, resources. The economic theory of mineral-resource conservation can be labeled variously as the theory of exhaustion, the theory of resource exploitation, the theory of resource utilization, or simply as a special case of the broad theory of capital.4,28 Consideration of these labels illuminates the concerns of the econo-

Jan 1, 1976

By Louis V. Bender

AfteR investigating the work of coal-dust fired reverberatories of the Canadian Copper Co., at Copper Cliff, Ontario, the management of the Washoe Reduction Works decided to experiment with and ascertain the advantages of using coal dust as a fuel in their reverberatories. Consequently, during the month of June, 1914, reverberatory furnace No. 8 was changed in order to use powdered coal as a fuel. The results obtained by this method of firing are gratifying and show a decided saving in cost of smelting as compared to grate firing with lump coal. The furnace, as remodeled, is 124 ft. long by 21 ft. wide, and varies in height from 8 ft. 6 in. at the back end to 5 ft. 7 in. at the skimming end. The general construction of the furnace is similar to that of the other furnaces at this plant. There are no side doors to this furnace, as it was thought that with the present arrangement for feeding no "fettling" or "claying" would be required. The interior of the furnace can be inspected through the burner port holes, after shutting off the burners and giving a few seconds' time for the gases inside the furnace to clear away. The charging is done on either side of the furnace from longitudinal hoppers, extending a distance of 74 ft. from the back end of the furnace. Leading from the hoppers into the furnace are 6-in. pipes, spaced 191/4 in. apart, through which the charge is intermittently dropped. The charge is kept well above the slag line at all times; in this way the side walls are protected and no fettling is needed on this portion of the furnace. The remainder of the furnace requires fettling. After operating for three months, we found that the bricks were eaten into along each side wall from the skimming door back to the point where the charge had been dropped. The depth of this cutting away was 8 in. close to the front end and gradually tapered to zero at a distance of 50 ft., and was greatest on the side of the furnace having the larger flue connection. Hoppers will be put in for the entire length of furnace, from which fettling material will be dropped, to prevent this cutting. After the run of three months, the roof was in excellent condition. At the back of the furnace the bricks were not cut into at all; at 30 ft.

Jan 1, 1915

By Harold Markus, Arthur H. Grobe, Gerhard Derge

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study. has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from 1/2 to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.? After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been damped. The pH of the electrolyte was controlled? by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.10. Potentials were measured against a saturated calomel electrode connected. to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy's law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy's law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

By E. W. Shaw

Continued discussion of the paper of Roswell H. JOHNSON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 221 to 226. See also Bulletin No. 101, May, 1915, pp. 1157 to 1162. E. W. SHAW, Washington, D. C. (communication to the Secretary+). -With the word petrology-literally the science of rocks-being used primarily for igneous rocks, and with geophysics coming to mean the study of lavas and the rocks into which they solidify, contributions to the knowledge of the physical chemistry of sedimentary rocks, even though only ideas which may be used as working hypotheses, become most welcome. The forces which control the formation and subsequent history of the stratified portions of the earth's crust are so little known that no one has yet been able to settle finally the questions as to whether petroleum is of organic or inorganic origin; whether it originated far from its present position, or nearby. Yet both the chemical and physical problems of the rocks in which oil occurs seem to be more simple than those of the igneous rocks. The oil-bearing rocks of western Pennsylvania, for example, have in all probability never been subjected to a pressure exceeding 3,000 or 4,000 lb. to the square inch, nor to a temperature higher than 100° or 200° C. These pressures are considerably below the crushing strength of rocks, and the temperature far below their melting point. The igneous rocks,, on the other hand, have been affected by enormous pressures and very high temperatures and yet steady progress is being made in reproducing in the laboratory the conditions of their formation and subsequent modification within the earth. The solution of the sedimentary-rock problems would seem to be fully as important as those of igneous rocks, and yet we must content ourselves with reasoning backward and our inferences as to what has happened are oftentimes little more than guesses.1 One of the fundamental problems is the origin of the salt water in oil fields. Is the salt water fossil sea water; has it been formed by the solution o-f salts of various kinds from distinct beds, from disseminated par-ticles, and from the weathering of suitable grains in the rock; or is it of deep-seated origin? Its general resemblance to sea water points to the first, but the principles held by some concerning the free circulation of water throughout the earth's crust, and certain peculiarities of composition indicated by the few analyses available, seem out of harmony with such an explanation.

Jan 7, 1915

By C. E. Nelson

THE purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.* The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protec-

Jan 1, 1944

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By D. H. Davis

HAND picking was the earliest form of coal preparation, first practiced to improve the outward appearance of the coal being loaded and to remove any pieces that might appear objection- able to the buyer. It is still extensively practiced on the plus 1-in. sizes, and particularly on the plus 4-in. and larger sizes. The percentage of ash reduction that can be obtained by hand picking depends entirely upon the amount of free impurity occurring in the coal. In a particularly dirty seam, where a considerable quantity of rock occurs with the coal as mined, hand picking produces sizable reductions in ash. If the coal is prepared clean at the working face hand picking is a final check; in some cases, on the smaller sizes, it is practiced only to show that an effort is being made to prepare a clean product. Because of the variety and different methods of handling coal, the early plants were not always adapted for efficient hand picking. At most mines an attempt is made to remove the visual impurities at one or more of the following places in the surface plant:2 (1) in the tipple during screening; (2) on picking band, belt, or shaking conveyors;. (3) during the loading of the coal as it goes into the railroad car. Whatever the physical arrangements of the plant may be, the usual practice is to run the coal over the screen, picking table or boom at such a rate that each-piece of impurity is exposed to the view of the picker. Coal should be uniformly sized and spread out on the table so as not to exceed one particle in depth. The flow should be even in tonnage and the speed of travel should be from 30 to 60 ft. per minute and not 'exceed 80 ft. per minute. The dirtier the coal, the slower the speed required for a fixed number of pickers. Actually, picking capacity depends on the number of particles per minute that can be picked out and-rejected. The percentage of impurity removed is determined by this and the average weight of piece rejected. Handling a mixture of sizes from nut to the largest lump over the same picking table or conveyor is not conducive to efficient separation by hand picking because the lump hides the smaller impurities. Picking tables should not exceed 5 ft, in width, so that a picker on either side will be able to remove impurities from the center of

Jan 1, 1943

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By R. A., D. L. Sponseller, Flinn

Using specially del'eloped titanium nitride crucibles and a pressurized syslem, it has been possible to determine the solzibilitv of liquid calcium in liquid iron and iron-base alloys. At 2925°F the solubility is 0.032 wt pet Ca in pure iron. The solubility is increased by aluminum, carbon, nickel, and silicon additions, and lowered by additions of gold. An inflection in the calcium-solubility curve occurs as carbon is added to iron. At approximately 0.87 Wt pet Ca the CaC, phase replaces liquid calcium, and the calcium concentration de- creases as more carbon is added to the iron. The maximum solubility, 0.36 wt pet Ca, was obtained in iron containing 10.5 wt pet Si. The data have important implications regarding the use of calcium in process metallurgy, as well as providing an interesting test of theories of metallic solutions. Reasonably good agreement is found with theories of Alcock and Richardson and of Wagner, and criteria are suggested which permit these theories to be applied more readily to systems of this type. AT the present time relatively little is known about the factors influencing solubility in liquid metals. Information of this type is important for such matters as the control of impurity levels in liquid metals, the use of magnesium in ductile-iron production, and the use of liquid-metal alloys as fuels and coolants in nuclear power plants. One important example of restricted solubility concerns the extent to which liquid calcium will dissolve in liquid iron. This is a matter of considerable interest in view of the strong potential of calcium for removing certain impurities in steel,. as well as the ability of calcium to desulfurize, inoculate, and produce spheroidal graphite in cast irons.' Since ferrous materials normally contain other elements in addition to iron, the interactions of third elements with the Fe-Ca system are of interest. In view of the foregoing, this investigation was conducted to determine the solubility of liquid calcium in liquid iron and the effects of various third elements upon the solubility. For reasons of theoretical and engineering importance, the elements investigated were aluminum, carbon, gold, nickel, and silicon. Numerous attempts were made in the early part of the present century to determine the solubility of calcium in both liquid iron and steel, employing a variety of open-melt and closed bomb-type systems.2-4 From the results of these tests Wever concluded that calcium is insoluble in liquid and solid iron.5 These investigations were unsatisfactory in that they failed to insure the presence of a liquid layer

Jan 1, 1964